CN105683828B - Aligning agent for liquid crystal, liquid crystal orientation film and liquid crystal indicate element - Google Patents

Aligning agent for liquid crystal, liquid crystal orientation film and liquid crystal indicate element Download PDF

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CN105683828B
CN105683828B CN201480059922.8A CN201480059922A CN105683828B CN 105683828 B CN105683828 B CN 105683828B CN 201480059922 A CN201480059922 A CN 201480059922A CN 105683828 B CN105683828 B CN 105683828B
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liquid crystal
aligning agent
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CN105683828A (en
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野田尚宏
芦泽亮
芦泽亮一
后藤耕平
桥本淳
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Nissan Chemical Corp
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    • C07C217/00—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton
    • C07C217/78—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton
    • C07C217/80—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of non-condensed six-membered aromatic rings
    • C07C217/82—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of non-condensed six-membered aromatic rings of the same non-condensed six-membered aromatic ring
    • C07C217/84—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of non-condensed six-membered aromatic rings of the same non-condensed six-membered aromatic ring the oxygen atom of at least one of the etherified hydroxy groups being further bound to an acyclic carbon atom
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    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1075—Partially aromatic polyimides
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    • C09D179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C09D179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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    • C09K19/00—Liquid crystal materials
    • C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
    • C09K19/54—Additives having no specific mesophase characterised by their chemical composition
    • C09K19/56—Aligning agents
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    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
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    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
    • G02F1/133703—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by introducing organic surfactant additives into the liquid crystal material
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    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
    • G02F1/133711—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films

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Abstract

The liquid crystal that the present invention provides fast response time indicates that element, particularly PSA type liquid crystal indicate the aligning agent for liquid crystal for being suitable in element.A kind of aligning agent for liquid crystal, which is characterized in that contain the polymer with side-chain structure shown in following formula (I)s.(I) (Ar indicates aromatic hydrocarbyl；R1、R2Indicate the alkyl etc. of carbon atom number 1~10；T1、T2Indicate singly-bound etc.；S indicates singly-bound etc.；Q indicates following structures) (II) (R indicates hydrogen atom etc.；R3Expression-CH2Etc.).

Description

Aligning agent for liquid crystal, liquid crystal orientation film and liquid crystal indicate element
Technical field
The present invention relates to the vertical orientations made by irradiation ultraviolet light in the state of applying voltage to liquid crystal molecule The liquid crystal of mode indicates that the aligning agent for liquid crystal that can be used in element etc., liquid crystal orientation film and liquid crystal indicate element.
Background technique
About by electric field make the liquid crystal molecule relative to substrate vertical orientation generate response in the way of it is (also referred to as vertical (VA) mode of orientation) liquid crystal indicate element, include that ultraviolet light is irradiated when applying voltage to liquid crystal molecule in manufacturing process Process.
Liquid crystal about this vertical orientation mode indicates element, it is known that following technology: adds in a liquid crystal composition in advance Add photopolymerizable compound, and using the vertical alignment layer of polyimides system etc., liquid crystal cells are irradiated when applying voltage Ultraviolet light, to accelerate technology (PSA (the Polymer Sustained Alignment of liquid crystal response speed；Polymer stabilizing Orientation) mode element, referring for example to patent document 1 and non-patent literature 1.).
In above-mentioned PSA mode element, in general, in response to electric field liquid crystal molecule inclined direction by being arranged on substrate The control of the slit being arranged in protrusion, expression electrode etc., and by adding photopolymerizable compound simultaneously into liquid-crystal composition Ultraviolet light is irradiated when applying voltage to liquid crystal cells, so that the inclined direction for forming liquid crystal molecule on liquid crystal orientation film is remembered The polymer architecture object recalled, therefore compared with merely with the method for protrusion, the inclined direction of slit control liquid crystal molecule, it is said that Liquid crystal indicates that the response speed of element becomes faster.
On the other hand, the liquid crystal of the PSA mode indicates in element that there are the dissolutions of the polymerizable compound added in liquid crystal Property it is low, it is precipitated etc in low temperature when increasing additive amount the problem of, and when reducing the additive amount of polymerizable compound, can not obtain Obtain good state of orientation.In addition, the impurity that remaining unreacted polymerizable compound can become in liquid crystal in liquid crystal is (dirty Dye), therefore there is also so that liquid crystal is indicated the problem of component reliability reduces.In addition, the photograph of UV treatment with irradiation needed for PSA mode When the amount of penetrating is more, the ingredient in liquid crystal decomposes and reliability is caused to reduce.
In turn, it was recently reported that: by adding photopolymerizable compound, liquid crystal watch to liquid crystal orientation film rather than in liquid-crystal composition Show that the response speed of element also becomes faster (SC-PVA type liquid crystal display, referring for example to non-patent literature 2).
Existing technical literature
Patent document
Patent document 1: Japanese Unexamined Patent Publication 2003-307720 bulletin
Non-patent literature
Non-patent literature 1:K.Hanaoka, SID 04DIGEST, P.1200-1202
Non-patent literature 2:K.H Y.-J.Lee, SID 09DIGEST, P.666-668
Summary of the invention
Problems to be solved by the invention
In recent years, indicate that the quality of element improves with liquid crystal, it is expected that further speeding up liquid crystal to applying alive response Speed.For this reason, it may be necessary to make polymerizable compound efficiency by the ultraviolet light irradiation for being not accompanied by the long wavelength of ingredient breakdown in liquid crystal It reacts well, plays orientation immobilization ability.In turn, it is also necessary to the not polymerism of remained unreacted after uv irradiation Object is closed, the reliability of element, which causes adverse effect, not to be indicated to liquid crystal.
The issue of the present invention is to provide can be improved the polymerism chemical combination made in liquid crystal and/or in liquid crystal orientation film Object reaction process obtained from liquid crystal indicate element response speed and be not accompanied by above-mentioned prior art problem liquid crystal aligning Agent, liquid crystal orientation film and liquid crystal indicate element.
The solution to the problem
The inventors of the present invention have made intensive studies, as a result, it has been found that, the polymer for constituting aligning agent for liquid crystal is directed through Ultraviolet light irradiates and the specific structure that generates free radicals, and by using the aligning agent for liquid crystal, improving use makes in liquid crystal and/or liquid Liquid crystal obtained from the process of polymerizable compound reaction in brilliant alignment films indicates the reaction of the polymerizable compound in element Property, thus, it is possible to reach the above subject, complete the present invention.
That is, the present invention has main idea below.
(1) a kind of aligning agent for liquid crystal, which is characterized in that contain the polymer with side-chain structure shown in following formula (I)s.
(Ar indicates the aromatic hydrocarbyl in phenylene, naphthylene and biphenylene, is optionally substituted on these alkyl Organic group, hydrogen atom are optionally substituted with halogen atoms.R1、R2Be separately the alkyl of carbon atom number 1~10, alkoxy, Benzyl or phenethyl, in the case where alkyl and/or alkoxy, optionally by R1、R2Form ring.T1、T2It is separately single Key ,-O- ,-COO- ,-OCO- ,-NHCO- ,-CONH- ,-NH- ,-CH2O-、-N(CH3)-、-CON(CH3)-or-N (CH3)CO-。S For singly-bound or alkylidene (the wherein ,-CH of alkylidene of carbon atom number 1~20 that is unsubstituted or being replaced by fluorine atoms2Or CF2Optional use-CH=CH- displacement, in addition, in the case where following any group is not adjacent to each other optionally by these groups Displacement :-O- ,-COO- ,-OCO- ,-NHCO- ,-CONH- ,-NH-, divalent carbocyclic ring or bivalent heterocyclic.).Q indicates following structures.
(R indicates the alkyl of hydrogen atom or carbon atom number 1~4, R3Expression-CH2,-NR- ,-O- or-S-.)
(2) aligning agent for liquid crystal according to above-mentioned (1), wherein the aforementioned polymerization with side-chain structure shown in formula (I) Object is selected from as the polyimide precursor with side-chain structure shown in aforementioned formula (I) and by polyamides obtained from its imidizate At least one of the group of imines composition polymer.
(3) aligning agent for liquid crystal according to above-mentioned (1) or (2), wherein the Ar in formula (I) is phenyl, and Q is-OR.
(4) aligning agent for liquid crystal according to any one of above-mentioned (1)~(3), wherein above-mentioned polymer also has and makes liquid Brilliant vertically oriented side chain.
(5) aligning agent for liquid crystal according to above-mentioned (4), wherein the above-mentioned side chain for making liquid crystal vertical-tropism is under State at least one of formula (II-1) and (II-2).
(X1Indicate singly-bound ,-(CH2)a(integer that a is 1~15) ,-O- ,-CH2O- ,-COO- or OCO-.X2Indicate singly-bound Or (CH2)b(integer that b is 1~15).X3Indicate singly-bound ,-(CH2)c(integer that c is 1~15) ,-O- ,-CH2O-、-COO- Or OCO-.X4Indicate that the bivalent cyclic group in phenyl ring, cyclohexane ring and heterocycle, the arbitrary hydrogen of these cyclic groups are former Son optionally by the alkyl of carbon number 1~3, the alkoxy of carbon number 1~3, carbon number 1~3 the fluorine-containing alcoxyl containing fluoroalkyl, carbon number 1~3 Base or fluorine atom replace, and X4The divalent in organic group optionally selected from the carbon number 17~51 with steroid skeleton has Machine group.X5Indicate the bivalent cyclic group in phenyl ring, cyclohexane ring and heterocycle, the arbitrary hydrogen on these cyclic groups Atom optionally by the alkyl of carbon number 1~3, the alkoxy of carbon number 1~3, carbon number 1~3 containing fluoroalkyl, carbon number 1~3 contain fluothane Oxygroup or fluorine atom replace.N indicates 0~4 integer.X6Indicate that the alkyl of carbon number 1~18, carbon number 1~18 contain fluoroalkyl, carbon The alkoxy of number 1~18 or the fluoroalkoxy of carbon number 1~18.)
——x7——x8 [II-2]
(X7Indicate singly-bound ,-O- ,-CH2O-、-CONH-、-NHCO-、-CON(CH3)-、-N(CH3) CO- ,-COO- or OCO-。X8Indicate carbon number 8~22 alkyl or carbon number 6~18 contain fluoroalkyl.)
(6) aligning agent for liquid crystal according to any one of above-mentioned (1)~(4), wherein above-mentioned polymer also has structure In the side chain containing photoreactive group.
(7) aligning agent for liquid crystal according to above-mentioned (6), wherein contain the side chain of photoreactive group in above structure It is indicated by following (III) or formula (IV).
——R8——R9——R10 [III]
(R8Indicate singly-bound ,-CH2-、-O-、-COO-、-OCO-、-NHCO-、-CONH-、-NH-、-CH2O-、-N(CH3)-、- CON(CH3)-or-N (CH3)CO-。R9The alkylidene of expression singly-bound, the carbon number 1~20 being optionally replaced by fluorine atoms, alkylidene- CH2Optional use-CF2Or-CH=CH- is arbitrarily replaced, in the case where following any group is not adjacent to each other optionally by this A little group displacements :-O- ,-COO- ,-OCO- ,-NHCO- ,-CONH- ,-NH-, divalent carbocyclic ring or heterocycle.R10It indicates selected from following Photoreactive group in formula.)
-Y1-Y2-Y3-Y4-Y5-Y6 (IV)
(Y1Expression-CH2,-O- ,-CONH- ,-NHCO- ,-COO- ,-OCO- ,-NH- or-CO-.Y2For carbon number 1~30 Alkylidene, divalent carbocyclic ring perhaps the heterocycle alkylidene, divalent carbocyclic ring or heterocycle one or more hydrogen atoms optionally by fluorine original Son or organic group replace.Y2- the CH in the case where following group is not adjacent to each other2Optionally replaced by these groups :- O-、-NHCO-、-CONH-、-COO-、-OCO-、-NH-、-NHCONH-、-CO-。Y3Expression-CH2-、-O-、-CONH-、- NHCO- ,-COO- ,-OCO- ,-NH- ,-CO- or singly-bound.Y4Indicate cinnamoyl.Y5For singly-bound, the alkylidene of carbon number 1~30, two One or more hydrogen atoms of valence carbocyclic ring perhaps the heterocycle alkylidene, divalent carbocyclic ring or heterocycle are optionally by fluorine atom or organic Group replaces.Y5- the CH in the case where following group is not adjacent to each other2Optionally replaced by these groups :-O- ,-NHCO- ,- CONH-、-COO-、-OCO-、-NH-、-NHCONH-、-CO-。Y6It indicates polymerism group, is acryloyl group or methyl-prop Enoyl-.)
(8) aligning agent for liquid crystal according to any one of above-mentioned (1)~(7), wherein above-mentioned polymer contains: making to contain Polyimide precursor obtained from thering is the diamine component of diamines shown in following formula (1) to react with tetracarboxylic dianhydride's ingredient and by its At least one of polyimides polymer obtained from imidizate.
The definition of symbol in formula is identical as above-mentioned formula (I).
(9) aligning agent for liquid crystal according to above-mentioned (8), wherein above-mentioned polymer also contains: make containing following formula (2) Shown in diamines diamine component reacted with tetracarboxylic dianhydride's ingredient obtained from polyimide precursor and by its imidizate and At least one of obtained polyimides polymer.
(X indicates the structure of above-mentioned formula [II-1] or formula [II-2], and n indicates 1~4 integer.)
(10) aligning agent for liquid crystal according to above-mentioned (8) or (9), wherein above-mentioned polymer also contains: making containing following Polyimide precursor obtained from the diamine component of diamines shown in formula (3) or (4) is reacted with tetracarboxylic dianhydride's ingredient and by its At least one of polyimides polymer obtained from imidizate.
(R8、R9And R10Definition it is identical as above-mentioned formula (III).)
(definition of Y1, Y2, Y3, Y4, Y5 and Y6 are identical as above-mentioned formula (IV).)
(11) aligning agent for liquid crystal according to any one of above-mentioned (8)~(10), wherein diamines shown in above-mentioned (1) For 10 moles of %~80 mole % of whole diamine components.
(12) aligning agent for liquid crystal according to any one of above-mentioned (1)~(11), wherein aligning agent for liquid crystal is used in liquid Simultaneously the irradiation of side application voltage lateral dominance ultraviolet light makes above-mentioned polymerism in crystalline substance and/or containing polymerizable compound in liquid crystal orientation film Liquid crystal obtained from compound reaction indicates element.
(13) a kind of liquid crystal orientation film, the aligning agent for liquid crystal as described in any one of above-mentioned (1)~(12) obtain.
(14) a kind of liquid crystal indicates element, has liquid crystal orientation film described in above-mentioned (13).
(15) liquid crystal according to above-mentioned (14) indicates element, wherein liquid crystal indicates that element is that side applies voltage lateral dominance Obtained from reacting above-mentioned polymerizable compound with ultraviolet light irradiation.
(16) a kind of polymer is the polyimide precursor containing side-chain structure shown in following formula (I)s and by its acyl At least one of polyimides polymer obtained from imidization.
In formula, R1、R2、T1、T2, S, Q, R definition and above-mentioned formula (I) it is same.
(17) a kind of diamines is indicated by following formula (I)s.
In formula, R1、R2、T1、T2, S, Q, R definition and above-mentioned formula (I) it is same.
(18) a kind of diamines, is indicated by following formula.
The effect of invention
According to the present invention, the liquid crystal for providing the vertical orientation mode of fast response time indicates element, particularly PSA type liquid crystal Indicate the aligning agent for liquid crystal for being suitable in element.Aligning agent for liquid crystal of the invention can in the ultraviolet light for having irradiated long wavelength The liquid crystal that enough manufactures substantially increase response speed indicates element.
Specific embodiment
Aligning agent for liquid crystal of the invention contains: side chain have above-mentioned formula (I) shown in structure at least one polymer (with It is also referred to as particular polymers down.) and solvent.Aligning agent for liquid crystal refers to the solution for being used to form liquid crystal orientation film, liquid crystal orientation film Refer to the film for being orientated liquid crystal along prescribed direction.
There is the polymer of structure shown in (I) as above-mentioned side chain, can be used makes containing shown in above-mentioned formula (IV) Polyimide precursor obtained from the diamine component of diamines is reacted with tetracarboxylic dianhydride's ingredient and will be obtained from its imidizate At least one of polyimides polymer.
It should be noted that diamine compound shown in above-mentioned formula (IV) (hereinafter also referred to specific diamines) is that document is unknown New compound.
<side chain generated free radicals is irradiated by ultraviolet light>
Particular polymers contained in aligning agent for liquid crystal of the invention have to be generated free radicals by ultraviolet light irradiation Position is as side chain.It can be indicated by following formula (I)s by the position that ultraviolet light irradiation generates free radicals.
In above-mentioned formula (I), the Ar that carbonyl is bonded is related to the absorbing wavelength of ultraviolet light, therefore when long wavelengthization, preferably The long structure of conjugate length as naphthylene, biphenylene.In addition, can replace substituted base on Ar, the substituent group is excellent It is selected as the organic group of electron as alkyl, hydroxyl, alkoxy, amino etc..
In formula (I), when Ar becomes structure as naphthylene, biphenylene, dissolubility is deteriorated, and the difficulty of synthesis also becomes It is high.When the wavelength of ultraviolet light is the range of 250nm~380nm, phenyl can also obtain sufficient characteristic, therefore most preferably phenyl.
In addition, R1、R2Independently of one another be carbon atom number 1~10 alkyl, alkoxy, benzyl or phenethyl, alkyl, It, can also be by R in the case where alkoxy1、R2Form ring.
In formula (I), Q is preferably the organic group of electron, preferably following.
(R indicates the alkyl of hydrogen atom or carbon atom number 1~4, R3Expression-CH2,-NR- ,-O- or-S-.)
In the case that Q is aminoderivative, when precursor, that is, polyamic acid polymerization of polyimides, generated carboxylic acid group It is likely to occur with a problem that amino forming salt, therefore more preferably hydroxyl or alkoxy.
As the polymer containing aligning agent for liquid crystal, using polyimide precursor and or polyimides, it is desirable to led to side chain When entering the structure of above-mentioned formula (I), from the treatability of raw material, the easness of the synthesis of polymer, it is preferred to use above-mentioned formula (I) Side-chain structure.
The position generated free radicals by ultraviolet light irradiation in above-mentioned formula (I) is specifically preferably following.From institute Obtained liquid crystal indicates to set out in terms of the reliability of element, particularly preferably (b) or (c).
It should be noted that in formula (I) ,-T1-S-T2Connection diaminobenzene is played to be produced from by ultraviolet light irradiation By the effect of the linking group at the position of base.T1、T2Separately for singly-bound ,-O- ,-S- ,-COO- ,-OCO- ,-NHCO- ,- CONH-、-NH-、-CH2O-、-N(CH3)-、-CON(CH3)-or-N (CH3)CO-.S is singly-bound or is optionally replaced by fluorine atoms Alkylidene (the wherein ,-CH of alkylidene of carbon atom number 1~202Or CF2It is optionally arbitrarily replaced with-CH=CH-, as follows Any group it is adjacent to each other in the case where optionally replaced by these groups :-O- ,-COO- ,-OCO- ,-NHCO- ,- CONH- ,-NH-, divalent carbocyclic ring or heterocycle.).Especially in terms of synthesizing difficulty, T2Most preferably-O-.In addition, Difficulty, deliquescent aspect are synthesized, S is preferably the alkylidene of the alkylidene that carbon number is 2~10, more preferably 4~8.
<side chain for making liquid crystal vertical-tropism>
Also have other than the preferably side chain shown in above-mentioned formula (I) of polymer contained in aligning agent for liquid crystal of the invention Make the side chain of liquid crystal vertical-tropism.Indicate the side chain of liquid crystal vertical-tropism by following formula [II-1] or formula [II-2].
X in formula [II-1]1、X2、X3、X4、X5And as n is as defined above.
Wherein, from the availability of raw material, the easness aspect of synthesis, X1Preferably singly-bound ,-(CH2)a(a 1 ~15 integer) ,-O- ,-CH2O- or COO-, more preferably singly-bound ,-(CH2)a(integer that a is 1~10) ,-O- ,-CH2O- Or COO-.Wherein, X2Preferably singly-bound or (CH2)b(integer that b is 1~10).Wherein, it sets out in terms of the easness of synthesis, X3Preferably singly-bound ,-(CH2)c(integer that c is 1~15) ,-O- ,-CH2O- or COO-, more preferably singly-bound ,-(CH2)c-(c Integer for 1~10) ,-O- ,-CH2O- or COO-.
Wherein, from the easness aspect of synthesis, X4Preferably phenyl ring, thiacyclohexane ring or with steroid skeleton The organic group of carbon number 17~51.Wherein, X5Preferably phenyl ring or thiacyclohexane ring.Wherein, from the availability of raw material, the appearance of synthesis It sets out in terms of Yi Du, n is preferably 0~3, more preferably 0~2.
Wherein, X6Preferably the alkyl of carbon number 1~18, carbon number 1~10 containing fluoroalkyl, carbon number 1~18 alkoxy or The fluoroalkoxy of carbon number 1~10.The more preferably alkoxy of the alkyl of carbon number 1~12 or carbon number 1~12.Particularly preferably carbon The alkyl of number 1~9 or the alkoxy of carbon number 1~9.
As the X in formula [II-1]1、X2、X3、X4、X5、X6And the preferred combination of n, it can enumerate and International Publication bulletin (2-1)~(2-629) phase recorded in 6~table of table 47 of page 13 of WO2011/132751 (2011.10.27 is disclosed)~page 34 Same combination.It should be noted that the X in each table of International Publication bulletin, in the present invention1~X6It is referred to as Y1~Y6, but Y1~ Y6 can use wording instead and say into X1~X6。
In addition, in (2-605) that is recorded in each table of International Publication bulletin~(2-629), it is solid with class in the present invention The organic group of the carbon number 17~51 of ol skeleton is referred to as the organic group with the carbon number 12~25 of steroid skeleton, but has The organic group of the carbon number 12~25 of steroid skeleton can use wording instead and say into the carbon number 17~51 with steroid skeleton Organic group.Wherein, preferably (2-25)~(2-96), (2-145)~(2-168), (2-217)~(2-240), (2-268) The combination of~(2-315), (2-364)~(2-387), (2-436)~(2-483) or (2-603)~(2-615).Particularly preferably Group be combined into (2-49)~(2-96), (2-145)~(2-168), (2-217)~(2-240), (2-603)~(2-606), (2- 607)~(2-609), (2-611), (2-612) or (2-624).
——x7——x8 [II-2]
In formula [II-2], X7、X8As defined above.Wherein, X7Preferably singly-bound ,-O- ,-CH2O-、-CONH-、- CON(CH3)-or COO-, more preferably singly-bound ,-O- ,-CONH- or COO-.Wherein, X8The preferably alkyl of carbon number 8~18.
As the side chain for making liquid crystal vertical-tropism, from can obtain high and stable liquid crystal vertical-tropism in terms of go out Hair is, it is preferable to use structure shown in formula [II-1].
It should be noted that having the ability root for making liquid crystal vertical-tropism of the polymer for the side chain for making liquid crystal vertical-tropism It is different according to the structure for the side chain for making liquid crystal vertical-tropism, typically, keep the amount of the side chain of liquid crystal vertical-tropism more, then makes The ability of liquid crystal vertical-tropism more improves, more few, more declines.In addition, there is ring compared with not having the case where cyclic structure In the presence of the higher tendency of ability for making liquid crystal vertical-tropism when shape structure.
<side chain of photoreactivity>
Can also have other than the side chain shown in above-mentioned formula (I) in polymer contained in aligning agent for liquid crystal of the invention There is the side chain of photoreactivity.The side chain of photoreactivity to be formed altogether with that can be reacted by the irradiation of the light such as ultraviolet light (UV) Functional group's (hereinafter also referred to photoreactive group of valence link.).
The side chain of photoreactivity can be bonded directly to the main chain of polymer, in addition it is also possible to carry out via linking group Bonding.The side chain of photoreactivity is for example indicated by following formula (III)s.
——R8——R9——R10 [III]
In formula (III), R8、R9、R10As defined above.Wherein, R8Preferably singly-bound ,-O- ,-COO- ,-NHCO Or-CONH-.R9It can use the method for common organic synthesis and formed, from the viewpoint of the easiness of synthesis, preferably The alkylidene of singly-bound or carbon number 1~12.
In addition, to R9Arbitrary-CH2Displaced divalent carbocyclic ring or heterocycle specifically show example below Son.
From photoreactivity aspect, R10Preferably methylacryloyl, acryloyl group or vinyl.
The amount of the side chain of photoreactivity is preferably capable being formed covalently by carrying out reaction using ultraviolet irradiation Key and the range for improving the response speed of liquid crystal are not influencing other characteristics to further speed up the response speed of liquid crystal It is preferably more as much as possible in range.
<polymer for forming aligning agent for liquid crystal>
Manufacture have specific side chain polyimide precursor and by polyamides made of the polyimide precursor imidizate Asia The method of amine is not particularly limited.For example, can enumerate: making the side that there is the diamines of specific side chain to polymerize with tetracarboxylic dianhydride Method；The method for polymerizeing the tetracarboxylic dianhydride containing specific side chain with diamine compound；After polymerizeing tetracarboxylic dianhydride with diamines, The compound-modified method etc. in polymer of specific side chain will be contained by arbitrarily reacting.Wherein, from the easiness of manufacture Viewpoint is set out, the method for polymerizeing the diamine compound containing specific side chain with tetracarboxylic dianhydride.
Polyamides about manufacture with specific side chain and with the side chain and/or photoreactivity side chain for making liquid crystal vertical-tropism Imines precursor and by the method for polyimides made of the polyimide precursor imidizate, can also enumerate with it is aforementioned same Method.Its preferred method similarly will preferably contain the diamine compound for making the side chain of liquid crystal vertical-tropism and/or contain The method for thering is the diamine compound of photoreactivity side chain to be polymerize with tetracarboxylic dianhydride.
<specific diamines>
Form diamines (hereinafter also referred to specific two used in the manufacture of the above-mentioned polymer of aligning agent for liquid crystal of the invention Amine.) have and the position generated free radicals is decomposed as side chain by ultraviolet light irradiation.
Ar, R in above-mentioned formula (I)1、R2、T1、T2And as Sn is as defined above.
Diaminobenzene in formula (I) can be the arbitrary structures based on o-phenylenediamine, m-phenylene diamine (MPD) or p-phenylenediamine, from The reactive aspect of acid dianhydride is set out, preferably m-phenylene diamine (MPD) or p-phenylenediamine.
As certain amines, from the easness of synthesis, versatility height, characteristic etc., most preferably shown in following formula Structure.It should be noted that the integer that n is 2~8 in formula.
<synthesis of specific diamines>
In the present invention, specific diamines can obtain as follows: being applied with by each step synthesis dinitro matrix or have can be The single nitro-body or diamines of the amino of the blocking group removed in reduction process are turned nitro using usually used reduction reaction It turns to amino or is deprotected blocking group, to obtain.
The synthetic method of diamine precursor has a various methods, such as synthesis described below is generated free radicals using ultraviolet light irradiation Position imports interval position, the method being then bonded with dinitrobenzene.It should be noted that the integer that n is 2~8 in formula.
In the case where above-mentioned reaction, using there are the substances of hydroxyl at two, but by the type of optimization alkali (catalyst), throw Expect ratio, synthesizes to the property of can choose.
It should be noted that used alkali is not particularly limited, preferably the inorganic bases such as potassium carbonate, sodium carbonate, cesium carbonate, Organic bases such as pyridine, dimethyl aminopyridine, trimethylamine, triethylamine, tri-n-butylamine etc..
Reduction diamine precursor, that is, dinitro compound method be not particularly limited, usually there are as below methods: using palladium carbon, Platinum oxide, Raney's nickel, platinum carbon, rhodium-aluminium oxide, vulcanization platinum carbon etc. are used as catalyst, in ethyl acetate, toluene, tetrahydrofuran, two In the solvent of oxane, alcohol system etc., the method that is restored using hydrogen, hydrazine, hydrogen chloride etc..Autoclave as needed etc..
On the other hand, in the case where containing unsaturated bond position in structure, if having unsaturation using palladium carbon, platinum carbon etc. Key position is reduced and is formed the worry of saturated bond, therefore as optimum condition, it is preferable to use reduced iron, tin, stannic chloride etc. Transition metal, poisoning palladium carbon and/or platinum carbon, the reducing condition as catalyst such as platinum carbon for mixing iron etc..
Alternatively, it is also possible to similarly using above-mentioned reduction process by being taken off with the diamino benzene derivant of the protections such as benzyl It protects and obtains diamines of the invention.
About specific diamines, it is preferable to use preferably 10~80 of diamine component used in the synthesis of polyamic acid rub You are %, more preferably 20~60 moles of %, particularly preferably 30~50 moles of %.
<diamines with the side chain for making liquid crystal vertical-tropism>
The side chain for making liquid crystal vertical-tropism is imported into the method for polyimides based polymer preferably at one of diamine component The diamines with specific side-chain structure is used in point.Particularly preferably using diamines (also referred to as specific side chain shown in following formula [2] Type diamine compound).
In formula [2], X indicates structure shown in previously described formula [II-1] or formula [II-2], and n indicates 1~4 integer, especially excellent It is selected as 1.
As specific side chain type diamine, from high and stable liquid crystal vertical-tropism aspect can be obtained, preferably Use diamines shown in following formula [2-1].
X in above-mentioned formula [2-1]1、X2、X3、X4、X5And n is each customized identical with above-mentioned formula [II-1], furthermore respectively Preferred configuration it is also each customized identical with above-mentioned formula [II-1].
It should be noted that in formula [2-1], integer that m is 1~4.Preferably 1 integer.
Specific side chain type diamine specifically can for example enumerate structure shown in following formula [2a-1]~formula [2a-31].
(R1Expression-O- ,-OCH2-、-CH2O-、-COOCH2Or CH2OCO-, R2For the straight-chain or branch of carbon number 1~22 Chain-like alkyl, the straight-chain of carbon number 1~22 or branched alkoxy, the straight-chain of carbon number 1~22 or branched it is fluorine-containing Alkyl or fluoroalkoxy.)
(R3Expression-COO- ,-OCO- ,-CONH- ,-NHCO- ,-COOCH2-、-CH2OCO-、-CH2O-、-OCH2Or CH2, R4For the straight-chain or branched-chain alkyl of carbon number 1~22, the straight-chain of carbon number 1~22 or branched alkoxy, carbon number 1~ 22 straight-chain or branched containing fluoroalkyl or fluoroalkoxy).
(R5Expression-COO- ,-OCO- ,-CONH- ,-NHCO- ,-COOCH2-、-CH2OCO-、-CH2O-、-OCH2-、- CH2,-O- or NH-, R6For fluorine-based, cyano, fluoroform alkyl, nitro, azo group, formoxyl, acetyl group, acetoxyl group or hydroxyl Base).
(R7For the straight-chain or branched-chain alkyl of carbon number 3~12, the cis-trans isomerization of 1 or 4 cyclohexylidene is respectively trans- Isomers).
(R8For the straight-chain or branched-chain alkyl of carbon number 3~12, the cis-trans isomerization of 1 or 4 cyclohexylidene is respectively trans- Isomers).
(A4Straight-chain or branched-chain alkyl for the carbon number 3~20 being optionally replaced by fluorine atoms, A3For 1,4- cyclohexylidene Or Isosorbide-5-Nitrae-phenylene, A2(associative key and A of " * " wherein, are indicated for oxygen atom or COO-*3Bonding), A1For oxygen atom or COO-* (wherein, indicate the associative key and (CH of " * "2)a2Bonding).In addition, a1For 0 or 1 integer, a2For 2~10 integer, a3For 0 or 1 integer).
In above-mentioned formula [2a-1]~[2a-31], particularly preferred formula [2a-1]~formula [2a-6], formula [2a-9]~formula [2a- 13] or formula [2a-22]~formula [2a-31].
In addition, following formula [2b- can be enumerated as the diamines with specific side-chain structure shown in previously described formula [II-2] 1] diamines shown in~[2b-10].
(A1It indicates the alkyl of carbon number 1~22 or contains fluoroalkyl).
In above-mentioned formula [2b-5]~formula [2b-10], A1Expression-COO- ,-OCO- ,-CONH- ,-NHCO- ,-CH2-、-O-、- CO- or NH-, A2Indicate the straight-chain or branched of the straight-chain of carbon number 1~22 or the alkyl of branched or carbon number 1~22 Contain fluoroalkyl.
Above-mentioned diamines can be according to liquid crystal aligning when being made liquid crystal orientation film, pre-tilt angle, voltage retention performance, accumulation The characteristics such as charge are using a kind or are mixed with two or more.
About the above-mentioned diamines with the side chain for making liquid crystal vertical-tropism, it is preferable to use used in the synthesis of polyamic acid 5~50 moles of % of diamine component, more preferably the 10~40 of diamine component mole %, particularly preferably 15~30 moles of %.
When using having the diamines of side chain for making liquid crystal vertical-tropism, fixed in the raising of response speed, the orientation of liquid crystal The aspect of change ability is especially excellent.
<diamines with photoreactivity side chain>
As the diamines of the side chain with photoreactivity, for example, there is the diamines of side chain shown in formula (3), specifically Diamines shown in the following general formula (3) can be enumerated, but is not limited to these.
(the R in formula (3)8、R9And R10It is identical to be as defined above the formula of stating (III).)
Two amino (- NH in formula (3)2) bonding position do not limit.Specifically, the linker relative to side chain Group, can enumerate 2 on phenyl ring, 3 position, 2,4 position, 2,5 position, 2,6 position, 3,4 position, 3,5 position It sets.Wherein, preferably 2 reactivity when synthesizing polyamides acid, 4 position, 2,5 position or 3,5 position. When also allowing for easiness when synthesizing diamines, more preferably 2,4 position or 3,5 position.
The diamines of side chain with photoreactivity can specifically enumerate substance below.
(X9、X10The linking group as singly-bound ,-O- ,-COO- ,-NHCO- or-NH- is each independently represented, Y indicates to appoint Select the alkylidene for the carbon number 1~20 being replaced by fluorine atoms.)
In addition, the diamines as the side chain with photoreactivity, can also enumerate shown in following formula has hair in side chain The diamines of the group of the group and generation photopolymerization reaction of third contact of a total solar or lunar eclipse dimerization reaction.
In above-mentioned formula, Y1Expression-CH2,-O- ,-CONH- ,-NHCO- ,-COO- ,-OCO- ,-NH- or-CO-.Y2For carbon number One or more hydrogen atoms of 1~30 alkylidene, divalent carbocyclic ring perhaps the heterocycle alkylidene, divalent carbocyclic ring or heterocycle are optional Replaced by fluorine atom or organic group.Y2- the CH in the case where following group is not adjacent to each other2Optionally set by these groups It changes :-O- ,-NHCO- ,-CONH- ,-COO- ,-OCO- ,-NH- ,-NHCONH- ,-CO-.Y3Expression-CH2-、-O-、-CONH-、- NHCO- ,-COO- ,-OCO- ,-NH- ,-CO- or singly-bound.Y4Indicate cinnamoyl.Y5For singly-bound, the alkylidene of carbon number 1~30, two One or more hydrogen atoms of valence carbocyclic ring perhaps the heterocycle alkylidene, divalent carbocyclic ring or heterocycle are optionally by fluorine atom or organic Group replaces.Y5- the CH in the case where following group is not adjacent to each other2Optionally replaced by these groups :-O- ,-NHCO- ,- CONH-、-COO-、-OCO-、-NH-、-NHCONH-、-CO-。Y6It indicates polymerism group, is acryloyl group or methyl-prop Enoyl-.
The diamines of the above-mentioned side chain with photoreactivity can be according to liquid crystal aligning when being made liquid crystal orientation film, pre-dumping The characteristics such as angle, voltage retention performance, accumulated charge are made liquid crystal and indicate the response speed of liquid crystal etc. when element and use a kind Or it is mixed with two or more.
In addition, about the side chain with photoreactivity diamines, it is preferable to use polyamic acid synthesis used in diamines 10~70 moles of % of ingredient, more preferably 20~60 moles of %, particularly preferably 30~50 moles of %.
<other diamines>
It should be noted that when manufacture polyimide precursor and/or polyimides, in the model for not damaging effect of the invention The interior other diamines that can be applied in combination in addition to above-mentioned diamines are enclosed as diamine component.Specifically, for example, can enumerate: P-phenylenediamine, 2,3,5,6- tetramethyl-para-phenylene diamine, 2,5- dimethyl-p-phenylenediamine, m-phenylene diamine (MPD), 2,4- dimethyl isophthalic two Amine, 2,5- diaminotoluene, 2,6- diaminotoluene, 2,5- diaminophenol, 2,4- diaminophenol, 3,5- diaminobenzene Phenol, 3,5- diamino benzyl alcohol, 2,4- diamino benzyl alcohol, 4,6- diamino resorcin, 4,4 '-benzidines, 3,3 '- Dimethyl -4,4 '-benzidine, 3,3 '-dimethoxy-4 's, 4 '-benzidines, 3,3 '-dihydroxy -4,4 '-diamino Biphenyl, 3,3 '-dicarboxyls -4,4 '-benzidine, 3,3 '-two fluoro- 4,4 '-biphenyl, 3,3 '-trifluoromethyls -4,4 '-diamino Base biphenyl, 3,4 '-benzidines, 3,3 '-benzidines, 2,2 '-benzidines, 2,3 '-benzidines, 4,4 '- Diaminodiphenyl-methane, 3,3 '-diaminodiphenyl-methanes, 3,4 '-diaminodiphenyl-methanes, 2,2 '-diamino hexichol Methylmethane, 2,3 '-diaminodiphenyl-methanes, 4,4 '-diamino-diphenyl ethers, 3,3 '-diamino-diphenyl ethers, 3,4 '-two Aminodiphenyl base ether, 2,2 '-diamino-diphenyl ethers, 2,3 '-diamino-diphenyl ethers, 4,4 '-sulfonyldianilines, 3,3 '- Sulfonyldianiline, bis- (4- aminophenyl) silane, bis- (3- aminophenyl) silane, bis- (4- aminophenyl) silane of dimethyl, Bis- (3- aminophenyl) silane of dimethyl, 4,4 '-phenothiazines, 3,3 '-phenothiazines, 4,4 '-diamino-diphenylamines, 3, 3 '-diamino-diphenylamines, 3,4 '-diamino-diphenylamines, 2,2 '-diamino-diphenylamines, 2,3 '-diamino-diphenylamines, N- methyl (4,4 '-diamino-diphenyl) amine, N- methyl (3,3 '-diamino-diphenyl) amine, N- methyl (3,4 '-diamino-diphenyl) Amine, N- methyl (2,2 '-diamino-diphenyl) amine, N- methyl (2,3 '-diamino-diphenyl) amine, 4,4 '-diamino hexichol first Ketone, 3,3 '-diaminobenzophenones, 3,4 '-diaminobenzophenones, 1,4- diaminonaphthalene, 2,2 '-diaminobenzophenones, 2,3 '-diaminobenzophenones, 1,5- diaminonaphthalene, 1,6- diaminonaphthalene, 1,7- diaminonaphthalene, 1,8- diaminonaphthalene, 2,5- Diaminonaphthalene, 2, bis- (4- aminophenyl) ethane of 6 diaminonaphthalenes, 2,7- diaminonaphthalene, 2,8- diaminonaphthalene, 1,2-, 1,2- are bis- Bis- (4- aminophenyl) propane of (3- aminophenyl) ethane, 1,3-, bis- (3- aminophenyl) propane of 1,3-, bis- (the 4- amino of 1,4- Phenyl) butane, bis- (3- aminophenyl) butane of 1,4-, bis- (3,5- diethyl -4- aminophenyl) methane, bis- (the 4- amino of 1,4- Phenoxy group) benzene, bis- (4- amino-benzene oxygen) benzene of 1,3-, bis- (4- aminophenyl) benzene of 1,4-, 1,3- bis- (4- aminophenyl) benzene, 1, Bis- (4- aminobenzyl) benzene of 4-, bis- (4- amino-benzene oxygen) benzene of 1,3-, 4,4 '-[1,4- phenylene is bis- (methylene)] diphenylamines, 4,4 '-[1,3- phenylene is bis- (methylene)] diphenylamines, 3,4 '-[1,4- phenylene is bis- (methylene)] diphenylamines, 3,4 '-[1, 3- phenylene is bis- (methylene)] diphenylamines, 3,3 '-[1,4- phenylene is bis- (methylene)] diphenylamines, 3,3 '-[1,3- phenylenes Bis- (methylene)] diphenylamines, 1,4- phenylene bis- [(4- aminophenyl) ketones], bis- [(3- aminophenyl) first of 1,4- phenylene Ketone], 1,3- phenylene bis- [(4- aminophenyl) ketones], 1,3- phenylene bis- [(3- aminophenyl) ketones], 1,4- phenylene Bis- (4-aminobenzoic acid esters), 1,4- phenylene bis- (3- Aminobenzoates), 1,3- phenylene bis- (4-aminobenzoic acid esters), 1,3- phenylene bis- (3- Aminobenzoates), bis- (4- aminophenyl) terephthalates, bis- (3- aminophenyls) are to benzene two Formic acid esters, bis- (4- aminophenyl) isophthalic acid esters, bis- (3- aminophenyl) isophthalic acid esters, N, the N '-(Asia 1,4- benzene Base) bis- (4- aminobenzamides), N, N '-(1,3- phenylene) bis- (4- aminobenzamides), N, N '-(1,4- phenylene) is double (3-AB), N, N '-(1,3- phenylene) bis- (3-ABs), N, N '-bis- (4- aminophenyls) is to benzene Diformamide, N, N '-bis- (3- aminophenyl) terephthalamides, N, N '-bis- (4- aminophenyl) isophtalamides, N, Bis- (3- aminophenyl) isophtalamides of N '-, bis- (4- aminophenyl) anthracenes of 9,10-, 4,4 '-bis- (4- amino-benzene oxygen) hexichol Base sulfone, 2,2 '-bis- [4- (4- amino-benzene oxygen) phenyl] propane, 2,2 '-bis- [4- (4- amino-benzene oxygen) phenyl] hexafluoropropane, 2,2 '-bis- (4- aminophenyl) hexafluoropropane, 2,2 '-bis- (3- aminophenyl) hexafluoropropane, 2,2 '-bis- (3- amino -4- methyl Phenyl) hexafluoropropane, 2,2 '-bis- (4- aminophenyl) propane, 2,2 '-bis- (3- aminophenyl) propane, 2,2 '-bis- (3- amino- 4- aminomethyl phenyl) propane, 3,5- diaminobenzoic acid, 2,5- diaminobenzoic acid, 1,3- bis- (4- amino-benzene oxygen) propane, 1, Bis- (3- amino-benzene oxygen) propane of 3-, bis- (4- amino-benzene oxygen) butane of 1,4-, 1,4- bis- (3- amino-benzene oxygen) butane, 1,5- Bis- (3- amino-benzene oxygen) pentanes of bis- (4- amino-benzene oxygen) pentanes, 1,5-, bis- (4- amino-benzene oxygen) hexanes of 1,6-, 1,6- are bis- Bis- (4- amino-benzene oxygen) heptane of (3- amino-benzene oxygen) hexane, 1,7-, 1,7- (3- amino-benzene oxygen) heptane, the bis- (4- of 1,8- Amino-benzene oxygen) octane, bis- (3- amino-benzene oxygen) octanes of 1,8-, bis- (4- amino-benzene oxygen) nonanes of 1,9-, bis- (the 3- ammonia of 1,9- Phenoxyl) nonane, 1,10- (4- amino-benzene oxygen) decane, 1,10- (3- amino-benzene oxygen) decane, 1,11- (4- aminobenzene Oxygroup) hendecane, 1,11- (3- amino-benzene oxygen) hendecane, 1,12- (4- amino-benzene oxygen) dodecane, 1,12- (3- amino Phenoxy group) aromatic diamines, bis- (4- aminocyclohexyl) methane, bis- (4- amino -3- methylcyclohexyl) methane such as dodecane etc. Ester ring type diamines, 1,3- diaminopropanes, 1,4- diaminobutane, 1,5- 1,5-DAP, 1,6- diamino hexane, 1,7- bis- Aminoheptane, 1,8- diamino-octane, 1,9- diamino nonane, 1,10- diamino decane, 1,11- diamino undecane, 1, The aliphatic diamines such as 12- diamino dodecane.
Above-mentioned other diamines can according to when being made liquid crystal orientation film liquid crystal aligning, pre-tilt angle, voltage retention performance, The characteristics such as accumulated charge are using a kind or are mixed with two or more.
<tetracarboxylic dianhydride>
The tetracarboxylic dianhydride's ingredient reacted with above-mentioned diamine component is not particularly limited.Specifically, can enumerate: benzene is equal Tetracid, 2,3,6,7- naphthalene tetracarboxylic acid, 1,2,5,6- naphthalene tetracarboxylic acid, 1,4,5,8- naphthalene tetracarboxylic acid, 2,3,6,7- anthracene tetrabasic carboxylic acid, 1,2, 5,6- anthracene tetrabasic carboxylic acid, 3,3 ', 4,4 '-biphenyltetracarboxyacid acids, 2,3,3 ', 4- biphenyltetracarboxyacid acid, bis- (3,4- dicarboxyphenyi) ethers, 3, 3 ', 4,4 '-benzophenone tetrabasic carboxylic acids, bis- (3,4- dicarboxyphenyi) sulfones, bis- (3,4- dicarboxyphenyi) methane, 2,2- it is bis- (3, 4- dicarboxyphenyi) propane, bis- (3,4- dicarboxyphenyi) propane of 1,1,1,3,3,3- hexafluoro -2,2-, bis- (3,4- dicarboxyl benzene Base) dimethylsilane, bis- (3,4- dicarboxyphenyi) diphenyl silanes, 2,3,4,5- pyridine tetrabasic carboxylic acid, bis- (the 3,4- dicarboxyls of 2,6- Base phenyl) pyridine, 3,3 ', 4,4 '-diphenyl sulfone tetrabasic carboxylic acids, 3,4,9,10- tetrabasic carboxylic acid, 1,3- diphenyl -1,2,3,4- ring Butane tetracarboxylic acid, oxygen two adjacent benzene tertacarbonic acid, 1,2,3,4- cyclobutane tetrabasic carboxylic acid, 1,2,3,4- pentamethylene tetrabasic carboxylic acid, 1,2,4,5- Cyclopentanetetracarboxylic, 1,2,3,4- tetramethyl -1,2,3,4- cyclobutane tetrabasic carboxylic acid, 1,2- dimethyl -1,2,3,4- cyclobutane four Carboxylic acid, 1,3- dimethyl -1,2,3,4- cyclobutane tetrabasic carboxylic acid, 1,2,3,4- cycloheptane tetrabasic carboxylic acid, 2,3,4,5- tetrahydrofuran four Carboxylic acid, 3,4- dicarboxyl -1- cyclohexyl succinic acid, 2,3,5- tricarboxylic cyclopentyl acetic acid, 3,4- dicarboxyl -1,2,3,4- four Hydrogen -1- naphthalene succinic, two rings [3,3,0] octane -2,4,6,8- tetrabasic carboxylic acid, two rings [4,3,0] nonane -2,4,7,9- tetrabasic carboxylic acid, Two rings [4,4,0] decane -2,4,7,9- tetrabasic carboxylic acid, two rings [4,4,0] decane -2,4,8,10- tetrabasic carboxylic acid, tricyclic [6.3.0.0 < 2,6 >] hendecane -3,5,9,11- tetrabasic carboxylic acid, 1,2,3,4- butane tetracarboxylic acid, 4- (2,5- dioxidotetrahydro furans -3- base) -1,2, 3,4- tetrahydronaphthalene -1,2- dicarboxylic acids, two rings [2,2,2] octyl- 7- alkene -2,3,5,6- tetrabasic carboxylic acid, 5- (2,5- dioxidotetrahydro furans Base) -3- methyl -3- thiacyclohexane -1,2- dicarboxylic acids, Fourth Ring [6,2,1,1,0,2,7] dodecane -4,5,9,10- tetrabasic carboxylic acid, 3,5, Tri- carboxyl norbornene -2:3,5:6 dicarboxylic acids of 6-, 1,2,4,5- cyclopentanetetracarboxylic etc..Certainly, tetracarboxylic dianhydride can also root Using a kind or 2 are applied in combination according to characteristics such as liquid crystal aligning, voltage retention performance, accumulated charges when liquid crystal orientation film is made Kind or more.
<polymerizable compound>
In aligning agent for liquid crystal of the invention, it can according to need and carry out photopolymerization or light containing having 2 or more ends The polymerizable compound of the group of crosslinking.The polymerizable compound is to have 2 or more to have progress photopolymerization or photo-crosslinking Group end compound.Herein, the polymerizable compound with the group for carrying out photopolymerization, which refers to have, passes through irradiation Light and the compound of functional group polymerizeing.In addition, the compound with the group for carrying out photo-crosslinking, which refers to, to be had and can lead to Cross irradiation light and with polymer, polyimide precursor and by the polyimide precursor imidizate selected from polymerizable compound Obtained from least one of polyimides polymer reacted and the compound of functional group that is crosslinked with them.It needs Illustrate, about have carry out photo-crosslinking group compound, have carry out photo-crosslinking group compound each other it Between also react.
With polymer, polymerism that the side chain with the side chain and photoreactivity that make liquid crystal vertical-tropism is used alone The case where compound, is compared, by the way that the aligning agent for liquid crystal of the invention for containing above-mentioned polymerizable compound is used for SC-PVA type liquid The liquid crystal of the vertical orientation modes such as crystal display indicates that element can significantly improve response speed, even if polymerizable compound adds Dosage is few also can sufficiently to improve response speed.
As the group for carrying out photopolymerization or photo-crosslinking, univalent perssad shown in following formula (IV)s can be enumerated.
(R12Indicate the alkyl of hydrogen atom or carbon number 1~4.Z1It indicates optionally by the alkyl of carbon number 1~12 or carbon number 1~12 Alkoxy replace divalent aromatic ring or heterocycle.Z2It indicates optionally by the alkyl of carbon number 1~12 or the alcoxyl of carbon number 1~12 The monovalence aromatic rings or heterocycle that base replaces.)
As the concrete example of polymerizable compound, can enumerate: shown in following formula (V)s 2 ends be respectively provided with into Have shown in the compound of the group of row photopolymerization, following formula (VI)s with carry out photopolymerization group end and have into The base of progress photo-crosslinking is respectively provided with shown in the compound of the end of the group of row photo-crosslinking, following formula (VII)s 2 ends The compound of group.
It should be noted that in following formula (V)s~(VII), R12、Z1And Z2With the R in above-mentioned formula (IV)12、Z1And Z2Phase Together, Q1For bivalent organic group.Q1It is preferred that having phenylene (- C6H4), biphenylene (- C6H4-C6H4), cyclohexylidene (- C6H10) etc. ring structures.Because the interaction with liquid crystal tends to get bigger.
The concrete example of polymerizable compound shown in formula (V) can enumerate polymerizable compound shown in following formula (4).Under It states in formula (4), V, W indicate singly-bound or-R1O-, R1For the alkylidene of the carbon number 1~10 of straight-chain or branched, preferably expression- R1O-, R1For the alkylidene of the carbon number 2~6 of straight-chain or branched.It should be noted that V, W can be identical or not Together, but when identical it is readily synthesized.
It should be noted that even there is acrylate-based, methyl-prop as the group for carrying out photopolymerization or photo-crosslinking The polymerizable compound of olefin(e) acid ester group rather than alpha-methylene-gamma-butyrolactone base has the acrylate-based, methacrylate The polymerizable compound that base clips the structure that oxyalkylene is bonded with phenylene at equal intervals also has α-methylene with above-mentioned two end Response speed similarly can be especially significantly increased in base-gamma-butyrolacton base polymerizable compound.In addition, having acrylic acid Ester group, methacrylate clip the polymerizable compound for the structure that oxyalkylene is bonded with phenylene at equal intervals to the steady of heat Qualitative raising, can substantially resistant to by high temperature, such as 200 DEG C or more of firing temperature.
The manufacturing method of above-mentioned polymerizable compound is not particularly limited, such as can manufacture according to following synthesis examples. For example, polymerizable compound shown in above-mentioned formula (4) can by Talaga shown in following reaction equations et al. in P.Talaga, The method of motion in M.Schaeffer, C.Benezra and J.L.Stampf, Synthesis, 530 (1990) uses SnCl22- (bromomethyl) acrylic acid (2- (bromomethyl) propenoic acid) is set to react and synthesize with aldehydes or ketones.It needs Illustrate, Amberlyst 15 is the strong-acid ion exchange resin of Rhom and Hass's manufacture.
(in formula, R ' indicates monovalent organic group.)
In addition, 2- (bromomethyl) acrylic acid can be existed by Ramarajan shown in following reaction equations et al. K.Ramarajan, K.Kamalingam, D.J.O ' Donnell and K.D.Berlin, Organic Synthesis, The method of motion in vol.61,56-59 (1983) and synthesize.
As specific synthesis example, synthesis V is-R1O-, W are-OR2And R1With R2Gather shown in identical above-mentioned formula (1) When conjunction property compound, 2 kinds of methods shown in following reaction equations can be enumerated.
In addition, synthesis R1With R2When polymerizable compound shown in different above-mentioned formulas (4), following reaction equations can be enumerated Shown in method.
In above-mentioned formula (4), when synthesis V and W is the polymerizable compound of singly-bound, side shown in following reaction equations can be enumerated Method.
<synthesis of polyamic acid>
When reacting to obtain polyamic acid, well known synthesis side can be used with tetracarboxylic dianhydride by diamine component Method.The method for reacting diamine component in organic solvent with tetracarboxylic dianhydride's ingredient.Diamine component and tetrabasic carboxylic acid two The reaction of acid anhydride is easier to carry out in organic solvent, and advantageous in terms of not generating by-product.
As organic solvent used in above-mentioned reaction, as long as polyamic acid generated can be dissolved, do not limit especially It is fixed.In turn, even the organic solvent of insoluble polyamic acid, the range that can also will not be precipitated in polyamic acid generated It is interior to be used in mixed way with above-mentioned solvent.It should be noted that the moisture in organic solvent interferes polymerization reaction, and then cause to be generated Polyamic acid hydrolysis, therefore, organic solvent preferably uses after dehydrating.
As organic solvent used in above-mentioned reaction, such as n,N-Dimethylformamide, N, N- dimethyl can be enumerated Acetamide, N, N- diethylformamide, N-METHYLFORMAMIDE, n-methyl-2-pyrrolidone, N- ethyl-2-pyrrolidone, 2- pyrrole Pyrrolidone, 1,3- dimethyl-2-imidazolinone, 3- methoxyl group-N, N- dimethylpropionamide, N- methyl caprolactam, dimethyl Sulfoxide, tetramethylurea, pyridine, dimethyl sulfone, hexamethyl sulfoxide, gamma-butyrolacton, isopropanol, methoxy amylalcohol, diamyl Alkene, ethylpentyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl Ketone, methyl cellosolve, the molten fibre of ethyl Agent, methylcellosolve acetate, butyl cellosolve acetate, ethyl cellosolve acetate, butyl carbitol, ethyl carbitol, Ethylene glycol, ethylene glycol acetate, ethyleneglycol monopropylether, ethylene glycol monobutyl ether, propylene glycol, Propylene glycol monoacetate, the third two The tertiary butyl ether of alcohol monomethyl ether, propylene glycol monobutyl ether, propylene glycol-, dipropylene glycol monomethyl ether, propylene glycol methyl ether acetate, diethyl two Alcohol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropyl Glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate list ether, dipropylene glycol monopropyl ether, dipropylene glycol list second Acid esters list propyl ether, 3- methyl -3- methoxybutyl acetic acid esters, tripropylene glycol methyl ether, 3- methyl -3- methoxybutanol, diisopropyl Ether, ethyl isobutyl ether, diisobutylene, pentyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methylcyclohexene, propyl ether, two are Ether, dioxanes, n-hexane, pentane, normal octane, diethyl ether, cyclohexanone, ethylene carbonate, propylene carbonate, methyl lactate, Ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propyleneglycolmethyletheracetate list ether, methyl pyruvate, ethyl pyruvate, 3- methoxy methyl propionate, 3- ethoxy-propionic acid Methylethyl, 3- methoxypropionate, 3- ethoxy-propionic acid, 3- methoxyl group Propionic acid, 3- methoxy propyl propyl propionate, 3- methoxy propyl acid butyl ester, diethylene glycol dimethyl ether, 4- hydroxy-4-methyl-2-pentanone, 2- Ethyl -1- hexanol etc..These organic solvents can be used alone or as a mixture.
The method for reacting diamine component in organic solvent with tetracarboxylic dianhydride's ingredient is following any Kind method: being stirred to diamine component is dispersed or dissolved in solution made of organic solvent, directly addition tetracarboxylic dianhydride Ingredient or the method that tetracarboxylic dianhydride's ingredient is dispersed or dissolved in organic solvent and added；Conversely, by tetracarboxylic dianhydride's ingredient It is dispersed or dissolved in organic solvent, the method for diamine component is added into obtained solution；Alternately addition tetracarboxylic dianhydride at Divide the method etc. with diamine component.In addition, when diamine component or tetracarboxylic dianhydride's ingredient include a variety of compounds, it can be pre- Make its reaction in the state of first being mixed, can also successively react one by one, low point obtained from can also reacting one by one Son amount body carries out hybrid reaction, and high molecular weight body is made.
Temperature when reacting diamine component with tetracarboxylic dianhydride's ingredient is, for example, -20 DEG C~150 DEG C, preferably -5 DEG C~ 100 DEG C of range.In addition, about reaction, for example, relative to reaction solution, the total concentration of diamine component and tetracarboxylic dianhydride's ingredient Preferably 1~50 mass %, more preferably 5~30 mass %.
Ratio of the total mole number of tetracarboxylic dianhydride's ingredient in above-mentioned polymerization reaction relative to the total mole number of diamine component Rate can be selected according to the molecular weight for the polyamic acid wanted.In the same manner as common polycondensation reaction, which is got over Close to 1.0, the molecular weight of polyamic acid generated more becomes larger, and is 0.8~1.2 if showing preferred range.
The method of polyamic acid used in the synthesis present invention is not limited to the above method, the conjunction with common polyamic acid Similarly at method, above-mentioned four are replaced using tetracarboxylic acid derivatives such as two carboxylic acid halides of the tetrabasic carboxylic acid of corresponding structure or tetrabasic carboxylic acid Carboxylic acid dianhydride is reacted by well known method, to can also obtain corresponding polyamic acid.
As the method that polyimides is made in above-mentioned polyamic acid imidizate, it can enumerate: directly heat polyamides The hot-imide of the solution of amino acid, the catalysis imidizate that catalyst is added in the solution of polyamic acid.It needs to illustrate It is that the acid imide rate from polyamic acid to polyimides need not be 100%.
By polyamic acid in the solution hot-imide when temperature be 100 DEG C~400 DEG C, preferably 120 DEG C~250 DEG C, preferably carried out while removing the water generated by imidization reaction to outside system.
The catalysis imidizate of polyamic acid can by adding basic catalyst and acid anhydrides in the solution of polyamic acid, It is stirred at -20~250 DEG C, preferably 0~180 DEG C, to carry out.The amount of basic catalyst be amide acidic group 0.5~ 30 moles times, preferably 2~20 moles times, 1~50 mole times, preferably 3~30 moles times that the amount of acid anhydrides is amide acidic group. As basic catalyst, pyridine, triethylamine, trimethylamine, tri-n-butylamine, trioctylamine etc. can be enumerated, wherein pyridine has for pushing away Appropriate alkalinity for into reaction, so it is preferred that.As acid anhydrides, acetic anhydride, trimellitic anhydride, benzenetetrahydride can be enumerated Deng, wherein when using acetic anhydride, purifying after reaction is become easy, so it is preferred that.It is catalyzed the imidizate of imidizate Rate can be controlled by adjusting catalytic amount and reaction temperature, reaction time.
In addition, poly amic acid ester can pass through tetracarboxylic acid acid diesters diacid chloride and same as the synthesis of above-mentioned polyamic acid two The reaction of amine；By tetracarboxylic acid acid diesters and with the same diamines of synthesis of above-mentioned polyamic acid condensing agent appropriate, alkali presence It is inferior to be reacted, to manufacture.In addition, by the pre-synthesis polyamic acid of the above method, using high molecular weight reactive by amide Carboxylic esterification in acid, it is also available.Specifically, for example, by tetracarboxylic acid acid diesters diacid chloride and diamines in alkali and organic molten It is reacted 30 minutes~24 hours, preferably 1 hour~4 hours at -20 DEG C~150 DEG C, preferably 0 DEG C~50 DEG C in the presence of agent, So as to synthesizing polyamides acid esters.In addition, poly amic acid ester is heated at high temperature, dealcoholysis is promoted to make its closed loop, thus It can obtain polyimides.
When the polyimide precursors such as autoreaction solution recycling polyamic acid generated, poly amic acid ester or polyimides, Precipitate it reaction solution investment lean solvent.As lean solvent used in precipitating, can enumerate methanol, acetone, oneself Alkane, butyl cellosolve, heptane, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), ethyl alcohol, toluene, benzene, water etc..Investment lean solvent is carried out The polymer of precipitating, can dry at normal temperature or heat drying under normal or reduced pressure after filtering and recycling.In addition, will return The polymer of receipts is dissolved in organic solvent again, again precipitating recycling, when such operation is repeated 2~10 times, it is possible to reduce Impurity in polymer.As lean solvent at this time, such as alcohols, ketone, hydrocarbon can be enumerated etc., it is selected using in them 3 kinds or more of lean solvent when, the efficiency of purifying further increases, so it is preferred that.
<aligning agent for liquid crystal>
Aligning agent for liquid crystal of the invention contains at least one polymer of the side chain with structure shown in above-mentioned formula (1), institute The content for stating polymer is preferably 1~20 mass %, more preferably 3~15 mass %, particularly preferably 3~10 mass %.Separately Outside, containing when 2 or more ends are respectively provided with the polymerizable compound for carrying out the group of photopolymerization or photo-crosslinking, content phase For above-mentioned 100 mass parts of polymer, preferably 1~50 mass parts, further preferably 5~30 mass parts.
In addition, aligning agent for liquid crystal of the invention can contain other polymer in addition to above-mentioned polymer.At this point, polymerization The content of other polymer in object whole components is preferably 0.5~80 mass %, more preferably 20~50 mass %.
The molecular weight of the polymer possessed by aligning agent for liquid crystal, the liquid obtained from view of coating of liquid crystalline alignment agent Crystalline substance orientation film strength and film formation when operability, the uniformity of film when, with pass through GPC (gel permeation chromatography；Gel Permeation Chromatography) the Weight-average molecular meter of method measurement is preferably 5000~1000000, more preferably 10000~150000.
Solvent contained by aligning agent for liquid crystal is not particularly limited, and side chain can be had structure shown in above-mentioned formula (1) Polymer and as needed and being respectively provided with 2 or more ends for containing carries out the polymerization of the group of photopolymerization or photo-crosslinking Property compound etc. contain the solvent of ingredient dissolution or dispersion.It is illustrated in the synthesis of above-mentioned polyamic acid for example, can enumerate Such organic solvent.Wherein, preferred n-methyl-2-pyrrolidone, gamma-butyrolacton, N- ethyl-from the viewpoint of dissolubility 2-Pyrrolidone, 1,3- dimethyl-2-imidazolinone, 3- methoxyl group-N, N- dimethylpropionamide.It is of course also possible to for 2 kinds with On mixed solvent.
Additionally, it is preferred that the uniformity of film will be improved, the solvent of flatness is mixed in aligning agent for liquid crystal contains ingredient The high solvent of dissolubility come using.As the solvent, such as can to enumerate isopropanol, methoxy amylalcohol, methyl molten Fine agent, ethyl cellosolve, butyl cellosolve, methylcellosolve acetate, butyl cellosolve acetate, ethyl cellosolve acetic acid Ester, butyl carbitol, ethyl carbitol, ethylcarbitol acetate, ethylene glycol, ethylene glycol acetate, ethylene glycol list isopropyl The tertiary fourth of ether, ethylene glycol monobutyl ether, propylene glycol, Propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol monobutyl ether, propylene glycol- Ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, two Propylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, propylene glycol methyl ether acetate, dipropylene glycol monoethyl ether, dipropyl two Alcohol monoacetate list ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate list propyl ether, 3- methyl -3- methoxybutyl second Acid esters, tripropylene glycol methyl ether, 3- methyl -3- methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, pentyl acetate, Butyl butyrate, butyl ether, diisobutyl ketone, methylcyclohexene, propyl ether, two ether, n-hexane, pentane, normal octane, diethyl ether, Methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propyleneglycolmethyletheracetate list ether, methyl pyruvate, third Keto acid ethyl ester, 3- methoxy methyl propionate, 3- ethoxy-propionic acid Methylethyl, 3- methoxypropionate, 3- ethoxy-propionic acid, 3- methoxypropionic acid, 3- methoxy propyl propyl propionate, 3- methoxy propyl acid butyl ester, 1- methoxy-2-propanol, 1- ethyoxyl -2- third Alcohol, 1- butoxy -2- propyl alcohol, 1- phenoxy group -2- propyl alcohol, Propylene glycol monoacetate, propylene-glycol diacetate, propylene glycol -1- are single Methyl ether -2- acetic acid esters, propylene glycol -1- list ether -2- acetic acid esters, dipropylene glycol, 2- (2- ethoxy-c oxygroup) propyl alcohol, lactic acid first Ester, ethyl lactate, lactic acid n-propyl ester, n-butyl lactate, isoamyl lactate, 2- ethyl -1- hexanol etc..These solvents can also mix It closes a variety of.These solvents are preferably 5~80 mass % of the entirety of solvent contained by aligning agent for liquid crystal, more preferably 20~60 matter Measure %.
In aligning agent for liquid crystal, ingredient other than the above can also be contained.It as its example, can enumerate: coating can be improved The compound of film thickness uniformity, surface smoothness when aligning agent for liquid crystal；The adaptation of liquid crystal orientation film and substrate can be improved Compound etc..
As the uniformity of film thickness, the compound of surface smoothness can be improved, fluorine system surfactant, organic can be enumerated Silicon-based surfactant, nonionic surfactants etc..More specifically, for example, can enumerate EFTOP EF301, EF303, EF352 (TOHKEM PRODUCTS CORPORATION manufacture), Megafac F171, F173, R-30 (DIC plants of formula meetings Society manufacture), FLUORAD FC430, FC431 (Sumitomo 3M Ltd. manufacture), AsahiGuard AG710, Surflon S- 382, SC101, SC102, SC103, SC104, SC105, SC106 (Asahi Glass Co., Ltd's manufacture) etc..These surfactants Use ratio relative to 100 mass parts of total amount of polymer contained in aligning agent for liquid crystal be preferably 0.01~2 mass parts, more Preferably 0.01~1 mass parts.
The concrete example of compound as the adaptation that can improve liquid crystal orientation film and substrate can enumerate silicon containing functionality The compound of alkane, compound containing epoxy group etc..For example, 3- TSL 8330,3- aminopropyl can be enumerated Triethoxysilane, 2- TSL 8330,2- aminopropyltriethoxywerene werene, N- (2- amino-ethyl) -3- TSL 8330, N- (2- amino-ethyl) -3- aminopropylmethyldimethoxysilane, 3- ureido-propyl front three Oxysilane, 3- ureidopropyltriethoxysilane, N- ethoxy carbonyl -3- TSL 8330, N- ethyoxyl Carbonyl -3-aminopropyltriethoxysilane, N- triethoxysilylpropyltetrasulfide diethylenetriamine, N- trimethoxy first silicon Alkyl propyl diethylenetriamine, three azepine decane of 10- trimethoxysilyl -1,4,7-, 10- triethoxy-silicane Three azepine decane of base -1,4,7-, 9- trimethoxysilyl -3,6- diaza nonyl acetic acid esters, 9- triethoxy-silicane Base -3,6- diaza nonyl acetic acid esters, N- benzyl -3- TSL 8330, three ethoxy of N- benzyl -3- aminopropyl Base silane, N- phenyl -3- TSL 8330, N- phenyl -3-aminopropyltriethoxysilane, N- are bis-, and (oxygen is sub- Ethyl) -3- TSL 8330, bis- (oxygen the ethylidene) -3-aminopropyltriethoxysilane of N-, the contracting of ethylene glycol two Water glycerin ether, polyethyleneglycol diglycidylether, propylene glycol diglycidylether, tripropyleneglycol diglycidyl ether, poly- the third two Alcohol diglycidyl ether, neopentylglycol diglycidyl ether, 1,6 hexanediol diglycidylether, glycerin diglycidyl ether, 2,2- dibromoneopentyl glycol diglycidyl ether, 1,3,5,6- four glycidyl group -2,4- hexylene glycol, N, N, N ', N '-four shrinks Glyceryl-m-xylene diamine, 1,3- bis- (N, N- diglycidyl amino methyl) hexamethylenes, N, N, N ' ,-four glycidol of N ' Base -4,4 '-diaminodiphenyl-methane, 3- (N- allyl-N- glycidyl) TSL 8330,3- (N, N- diglycidyl) TSL 8330 etc..
In addition, 2,2 '-bis- (4- hydroxyls -3,5- bis- can also be added in order to further increase the film-strength of liquid crystal orientation film Hyd roxymethyl phenyl) phenolic compounds such as propane, four (methoxy) bis-phenols.These compounds are relative to institute in aligning agent for liquid crystal 100 mass parts of total amount of the polymer contained are preferably 0.1~30 mass parts, more preferably 1~20 mass parts.
In turn, in aligning agent for liquid crystal, in addition to that mentioned above, as long as within the scope of the effect of the invention, Can for the electrical characteristics such as dielectric constant, electric conductivity for changing liquid crystal orientation film purpose and add dielectric, conductive materials.
The aligning agent for liquid crystal is coated on substrate and is burnt into, so as to form the liquid crystal aligning for making liquid crystal vertical-tropism Film.By using aligning agent for liquid crystal of the invention, it can be improved and the liquid crystal of obtained liquid crystal orientation film has been used to indicate element Response speed.In addition, what is optionally contained in aligning agent for liquid crystal of the invention is respectively provided with carry out photopolymerization 2 or more ends Or the polymerizable compound of the group of photo-crosslinking can not contain in aligning agent for liquid crystal or contain together with aligning agent for liquid crystal In liquid crystal, so that the light reaction also high-sensitivity under so-called PSA mode, also can using less ultraviolet irradiation amount Assign inclination angle.
For example, being dried as needed after aligning agent for liquid crystal of the invention is coated on substrate, it is burnt into, thus Cured film is obtained, which can also be directly used as liquid crystal orientation film.Alternatively, it is also possible to by the cured film friction or shine It penetrates the processing of light of polarised light or specific wavelength etc. or progress ion beam etc. or is filled with alignment films to liquid crystal as PSA Liquid crystal afterwards indicates to irradiate UV in the state that element applies voltage.It is useful for using especially as PSA alignment films.
At this point, as used substrate, as long as the substrate that the transparency is high, there is no particular limitation, glass can be used Glass plate, polycarbonate, poly- (methyl) acrylate, polyether sulfone, polyarylate, polyurethane, polysulfones, polyethers, polyether-ketone, trimethyl penta Alkene, polyolefin, polyethylene terephthalate, (methyl) acrylonitrile, triacetyl cellulose, diacetyl cellulose, acetic acid fourth Plastic bases such as acid cellulose etc..In addition, using the ITO electrode being formed with for liquid crystal drive etc. substrate when, from technique It is preferred from the perspective of simplification.In addition, the liquid crystal of reflection-type indicates in element, if being only unilateral substrate, Silicon Wafer It also can be used etc. opaque object, the material of the meeting reflected light such as aluminium also can be used in electrode at this time.
The coating method of aligning agent for liquid crystal is not particularly limited, and can enumerate silk-screen printing, hectographic printing, flexible version printing Deng print process, ink-jet method, spray-on process, rolling method, dipping, roll coater, slit coater, spinner etc..From the side of productivity Face sets out and hectographic printing method is industrially widely used, and can also properly use in the present invention.
It can be burnt by the film that above method coating of liquid crystalline alignment agent is formed and cured film is made.Coating fluid The process of drying after brilliant alignment agent is not required, but the time after coating until firing is not permanent for each substrate When periodically, or after coating not being burnt into immediately, process is preferably dried.As long as the drying removes solvent to will not be because of substrate Conveying etc. and the degree that makes film shape deform, are not particularly limited the drying means.For example, can enumerate Dry 0.5 minute~30 minutes, preferably 1 minute~5 minutes on the hot plate that 40 DEG C~150 DEG C, preferably 60 DEG C~100 DEG C of temperature Method.
The firing temperature of the film formed by coating of liquid crystalline alignment agent is not limited, and for example, 100~350 DEG C, excellent It is selected as 120~300 DEG C, further preferably 150 DEG C~250 DEG C.Firing time is 5 minutes~240 minutes, preferably 10 minutes ~90 minutes, more preferably 20 minutes~90 minutes.Heating can by generally well-known method, for example, hot plate, hot air circulation Furnace, infrared heating heating furnace etc. carry out.
In addition, the thickness of liquid crystal orientation film obtained from firing is not particularly limited, preferably 5~300nm, it is more preferably 10~100nm.
<liquid crystal expression element>
After liquid crystal of the invention indicates that element can form liquid crystal orientation film on substrate by the above method, by known Method and make liquid crystal cells.The concrete example that element is indicated as liquid crystal, there is the vertical orientation for having following liquid crystal cells The liquid crystal of mode indicates element, that is, the liquid crystal cells include 2 substrates of relative configuration, the liquid crystal being set between substrate Layer, the above-mentioned liquid crystal orientation film formed by aligning agent for liquid crystal of the invention being arranged between substrate and liquid crystal layer.Specifically, Element is indicated for the liquid crystal of the vertical orientation mode with the liquid crystal cells made as follows: by by aligning agent for liquid crystal of the invention It is coated on 2 substrates and is burnt into, and form liquid crystal orientation film, 2 substrates are configured in the opposite mode of the liquid crystal orientation film, The liquid crystal layer being made of liquid crystal is clamped between 2 substrates, that is, liquid crystal layer is set in a manner of contacting with liquid crystal orientation film, Ultraviolet light is irradiated while applying voltage to liquid crystal orientation film and liquid crystal layer, to make.
Using the liquid crystal orientation film formed by aligning agent for liquid crystal of the invention, liquid crystal orientation film and liquid crystal layer are applied on one side Voltage irradiates ultraviolet light on one side, polymerize polymerizable compound, and make the side chain of photoreactivity possessed by polymer each other, The side chain of photoreactivity possessed by polymer is reacted with polymerizable compound, to keep the orientation of liquid crystal more efficiently solid Fixedization, becoming the obvious excellent liquid crystal of response speed indicates element.
Substrate used in element is indicated as liquid crystal of the invention, is not limited especially as long as the high substrate of the transparency It is fixed, the substrate for driving the transparent electrode of liquid crystal is usually formed on substrate.As concrete example, can enumerate with it is above-mentioned The same substrate of the substrate recorded in liquid crystal orientation film.Also the existing substrate equipped with electrode pattern, projection pattern can be used, But liquid crystal of the invention indicates to have used the aligning agent for liquid crystal of aforementioned present invention, therefore form example on single sided substrate in element Such as 1~10 μm of line/gap electrode pattern and in the case where slit pattern not formed in counter substrate, the structure of projection pattern Also it can work, indicate element using the liquid crystal of the structure, technique when manufacture can be simplified, obtain high transmittance.
In addition, can be used in high function element as the element of TFT type in the electrode and substrate for liquid crystal drive Between be formed with the element as transistor liquid crystal indicate element.
In the case that the liquid crystal of transmission-type indicates element, usually used substrate as described above, but the liquid crystal watch of reflection-type Show in element, if being only unilateral substrate, the opaque substrate such as Silicon Wafer also can be used.At this point, being formed on substrate Electrode in, also can be used can reflected light the material as aluminium.
Constituting liquid crystal of the invention indicates that the liquid crystal material of the liquid crystal layer of element is not particularly limited, and can be used existing The minus such as MLC-6608, MLC-6609 of liquid crystal material, such as Merck&Co. used with vertical orientation mode, Inc. manufacture Liquid crystal.In addition, the liquid crystal containing such polymerizable compound shown in following formula can be used for example in PSA mode.
In the present invention, as method liquid crystal layer being clamped between 2 substrates, can enumerate well known method.For example, It can enumerate: prepare 1 pair of substrate for being formed with liquid crystal orientation film, spread microballon at equal intervals on the liquid crystal orientation film of a substrate Object, pastes another substrate in a manner of being formed with the face of side of liquid crystal orientation film as inside, and decompression injection liquid crystal is gone forward side by side The method of row sealing.Alternatively, it is also possible to make liquid crystal cells by following method: preparing 1 pair that is formed with liquid crystal orientation film Substrate spreads microballon on the liquid crystal orientation film of a substrate and liquid crystal is added dropwise after object at equal intervals, then to be formed with liquid crystal aligning The face of the side of film becomes the method that the mode of inside is pasted another substrate, and is sealed.The thickness of above-mentioned spacer is excellent It is selected as 1~30 μm, more preferably 2~10 μm.
The works of liquid crystal cells is made about ultraviolet light is irradiated while applying voltage to liquid crystal orientation film and liquid crystal layer Sequence, such as can enumerate: between voltage is applied the electrode being disposed on the substrate, to apply electricity to liquid crystal orientation film and liquid crystal layer , the method for ultraviolet light is irradiated in the state of keeping the electric field constant.Herein, as being applied to interelectrode voltage, such as For 5~30Vp-p, preferably 5~20Vp-p.Ultraviolet irradiation amount is, for example, 1~60J, preferably 40J hereinafter, ultraviolet light shines When the amount of penetrating is few, the reliability for being able to suppress the destruction due to the component for constituting liquid crystal expression element and occurring is reduced, and passes through It reduces ultraviolet irradiation time and improves manufacture efficiency, therefore be suitable.
As described above, when irradiating ultraviolet light while applying voltage to liquid crystal orientation film and liquid crystal layer, polymerism chemical combination Object reacts and forms polymer, using the direction of polymer memory liquid crystal molecules tilt, obtained by improving Liquid crystal indicate element response speed.In addition, irradiating ultraviolet light while applying voltage to liquid crystal orientation film and liquid crystal layer When, selected from have make liquid crystal vertical-tropism side chain and photoreactivity side chain polyimide precursor and will be before the polyimides The side chain of photoreactivity possessed by the polymer of at least one of polyimides obtained from body imidizate each other, polymerization The side chain of photoreactivity possessed by object reacts with polymerizable compound, therefore can be improved obtained liquid crystal expression member The response speed of part.
Embodiment
Hereinafter, being further elaborated with the present invention using embodiment, but the present invention is not completely by any limit of the embodiment It is fixed.
<synthesis of diamines>
(synthesis example 1)
Step 1:1- (4- (2,4- dinitrophenoxy) ethyoxyl) phenyl) -2- hydroxy-2-methyl acetone synthesis
In the 2L four-hole boiling flask for having stirrer and nitrogen ingress pipe, addition 2,4-dinitrofluorobenzene 100.0g ([Mw: 186.10g/mol], 0.538mol), 2- hydroxyl -4 '-(2- hydroxyl-oxethyl) -2- methyl phenyl ketone 120.6g ([Mw: 224.25g/mol], 0.538mol), triethylamine 81.7g ([Mw:101.19g/mol], 0.807mol), THF 1000g, reflux 24 hours.After reaction, it is concentrated with Rotary Evaporators, ethyl acetate is added, it is cleaned for several times with pure water and physiological saline Afterwards, it is dried with anhydrous magnesium sulfate.
Filtering removal anhydrous magnesium sulfate, after being concentrated with Rotary Evaporators, is recrystallized using ethyl acetate and n-hexane, Obtain milky solid 157.0g ([Mw:390.34g/mol], 0.402mol, yield: 75%).Utilize intramolecular hydrogen atom Nuclear magnetic resoance spectrum (1H-NMR spectrum) confirmation.Determination data described below.
1H NMR (400MHz, CDCl3) δ: 8.75 (Ar:1H), 8.48~8.45 (Ar:1H), 8.09~8.05 (Ar:2H), 7.34~7.31 (Ar:1H) 7.00~6.96 (Ar:2H), 4.65~4.63 (- CH2-:2H), 4.52~4.49 (- CH2-:2H), 4.16 (- OH:1H), 1.66~1.60 (- CH3 × 2,6H) Total:18H
Step 2 1- (4- (2,4- diamino phenoxy) ethyoxyl) phenyl) -2- hydroxy-2-methyl acetone (DA-1) conjunction At
Weighed in 1L four-hole boiling flask dinitrobenzene derivative 100.0g obtained in step 1 ([Mw:390.34g/mol], 0.256mol) and doped with iron platinum carbon (Evonic company manufacture 3wt%) 10.0g, THF 500ml is added, is sufficiently subtracted Pressure-off gas and hydrogen displacement, react 24 hours at room temperature.
After reaction, platinum carbon is removed with the molecular filter of PTFE, removes filtrate using Rotary Evaporators, analyses solid Out.Heating is carried out to obtained solid with isopropanol to clean, is then dried under reduced pressure, to obtain as the light of target compound Solid 72.7g ([Mw:330.38g/mol], the 0.220mol yield: 86%) of pink colour.It is described below1H-NMR composes determination data.
1H NMR (400MHz, CDCl3) δ: 8.09~8.05 (Ar:2H), 7.01~6.97 (Ar:2H), 6.70~6.68 (Ar:1H), 6.12 (Ar:1H), 4.36~4.33 (- CH2-:2H), 4.29~4.27 (- OH&-CH2-:3H), 3.7 (- NH2: 2H), 3.39 (- NH2:2H), 1.64~1.63 (- CH3 × 2:6H) Total:22H
(synthesis example 2)
The synthesis of step 1 2- (4- (2- hydroxy-2-methyl propiono) phenoxy group) ethyl 3,5- dinitrobenzoic acid ester
In the 2L four-hole boiling flask for having stirrer and nitrogen ingress pipe, it is added 2- hydroxyl -4 '-(2- hydroxyl-oxethyl) - 2- methyl phenyl ketone 100.0g ([Mw:224.25g/mol], 0.446mol), pyridine 118.6g ([Mw:79.10g/mol], 1.50mol), THF 1000g gradually marginally adds 3,5- dinitrobenzoyl chloride in the state of being kept for 10 DEG C or less 123.3g ([Mw:230.56g/mol], 0.535mol) restores room temperature and react within 12 hours after 30 minutes.Confirmation reaction terminates Afterwards, it is concentrated with Rotary Evaporators, ethyl acetate is added, is cleaned for several times with wet chemical (10% solution), then uses pure water After physiological saline cleaning for several times, it is dried with anhydrous magnesium sulfate.
Filtering removal anhydrous magnesium sulfate, is concentrated with Rotary Evaporators, obtains the liquid 162.3g of the yellow as object ([Mw:418.35g/mol], 0.388mmol, yield: 76%).It is described below1H-NMR composes determination data.
1H NMR (400MHz, CDCl3) δ: 9.24 (Ar:1H), 9.18 (Ar:2H), 8.10~8.07 (Ar:2H), 7.02~ 6.98 (Ar:2H), 4.86~4.84 (- CH2-:2H), 4.47~4.44 (- CH2-:2H), 4.15~4.10 (- OH:1H), 1.64 ~1.61 (- CH3 × 2:6H) Total:18H
Step 2 2- (4- (2- hydroxy-2-methyl propiono) phenoxy group) ethyl 3,5- diaminobenzoic acid ester (DA-2) Synthesis
Weighed in 1L four-hole boiling flask dinitrobenzene derivative 150.0g obtained in step 1 ([Mw:390.34g/mol], 0.384mol) with palladium carbon (the aqueous product of 5wt%) 10.0g, THF 500ml is added, sufficiently carries out decompression degassing and hydrogen displacement, It reacts 24 hours at room temperature.
After reaction, palladium carbon is removed with the molecular filter of PTFE, removes filtrate using Rotary Evaporators, analyses solid Out.The mixed solvent (weight ratio: 2:1) of obtained solid ethyl acetate and n-hexane is recrystallized, is depressurized It is dry, thus obtain the white as target compound solid 124.0g ([Mw:358.39g/mol], 0.346mol yield: 90%).It is described below1H-NMR composes determination data.
1H NMR (400MHz, d6- DMSO) δ: 8.21~8.20 (Ar:2H), 7.06~7.03 (Ar:2H), 6.45 (Ar: 2H), 6.40 (Ar:1H), 6.03 (- OH:1H), 5.01 (- NH2 × 2:4H), 4.53~4.52 (- CH2-:2H), 4.37~4.36 (- CH2-:2H), 1.39 (- CH3 × 2:6H) Total:22H
<preparation of aligning agent for liquid crystal>
Abbreviation below is as described below.
(acid dianhydride)
BODA: two rings [3,3,0] octane -2,4,6,8- tetracarboxylic dianhydride
CBDA:1,2,3,4- cyclobutane tetracarboxylic dianhydride
PMDA: trimellitic anhydride
TCA:2,3,5- tricarboxylic cyclopentyl acetic acid -1,4,2,3- dianhydride
(diamines)
M-PDA: m-phenylene diamine (MPD)
DBA:3,5- diaminobenzoic acid
3AMPDA:3,5- diamino-N-(pyridin-3-yl methyl) benzamide
4DABP: following 4,4 '-diaminobenzophenones
DA-1~DA-2: following free radicals obtained in synthesis example 1,2 generate diamines
DA-3~DA-4: following photoreactivity diamines
DA-6~DA-9: following vertical orientation diamines
<solvent>
NMP:N- N-methyl-2-2-pyrrolidone N
BCS: butyl cellosolve
<additive>
3AMP:3- pyridyl-methanamine
<polymerizable compound>
Polymerizable compound shown in following formula RM1, RM2
<liquid crystal containing polymerizable compound>
Polymerizable compound RM3 is added in Merck&Co., the negative type liquid crystal MLC-6608 (10.0g) of Inc. manufacture 30mg (being 0.3wt% relative to liquid crystal), makes it dissolve at 120 DEG C, prepares the liquid crystal (LC1) containing polymerizable compound.
<other>
IPDI: following isophorone diisocyanate shown
KIP150: polymer (the SYNASIA corporation for having free radical and causing function of following polystyrenes shown It makes)
<measurement of the molecular weight of polyimides>
Device: Senshu Scientific Co.Ltd. manufactures room temperature gel permeation chromatography (GPC) device (SSC- 7200)、
Column: the column (KD-803, KD-805) of Shodex company manufacture
Column temperature: 50 DEG C
Eluent: N, N '-dimethyl formamide is (as additive, lithium bromide hydrate (LiBrH2It O) is 30mmol/ L, phosphoric acid anhydrous crystalline (orthophosphoric acid) is 30mmol/L, tetrahydrofuran (THF) is 10ml/L)
Flow velocity: 1.0ml/ minutes
For making the standard sample of standard curve: the TSK standard polyethylene oxide (molecular weight of TOSOH Co., Ltd's manufacture About 9000000,150000,100000,30000) and Polymer Laboratory company manufacture polyethylene glycol (molecule Amount about 12000,4000,1000).
<measurement of the acid imide rate of polyimides>
Polyimide powder 20mg is put into NMR sample cell, and (wasteland's science Co., Ltd. manufactures NMR sampling tube Standard φ 5), add deuterated dimethyl sulfoxide (DMSO-d6, 0.05%TMS melange) 1.0ml, apply ultrasonic wave make it It is completely dissolved.NMR analyzer (the JNW- manufactured for the solution with Japan Electron Datum Corporation ECA500 the proton NMR of 500MHz) is measured.Acid imide rate using be originated from the proton of unconverted structure before and after imidizate as Reference proton determines, using the proton peak integrated value and appear in the NH base from amic acid near 9.5~10.0ppm Proton peak integrated value, found out according to following formula.It should be noted that x is the NH base from amic acid in following formula Proton peak integrated value, y are the peak integrated value of benchmark proton, and α is the benchmark in the case where polyamic acid (acid imide rate is 0%) Number ratio of the proton relative to the proton of the NH base of 1 amic acid.
Acid imide rate (%)=(1- α x/y) × 100
(embodiment 1)
By CBDA (1.86g, 10.0mmol), DA-1 (2.51g, 7.0mmol), DA-6 (1.14g, 3.0mmol) in NMP After carrying out reaction in 10 hours in (22.1g), NMP (36.8g) and BCS (27.6g) are added, stirs 5 hours, obtains aligning agent for liquid crystal (A)。
In addition, adding polymerizable compound RM1 0.06g (relative to solid for above-mentioned aligning agent for liquid crystal (A) 10.0g Ingredient is 10 mass %), at room temperature stir to dissolve within 3 hours, prepares aligning agent for liquid crystal (A1).
In addition, adding polymerizable compound RM2 0.06g (relative to solid for above-mentioned aligning agent for liquid crystal (A) 10.0g Ingredient is 10 mass %), at room temperature stir to dissolve within 3 hours, prepares aligning agent for liquid crystal (A2).
(embodiment 2)
By CBDA (1.86g, 10.0mmol), DA-1 (1.08g, 3.0mmol), DA-4 (1.06g, 4.0mmol), DA-7 After (1.30g, 3.0mmol) carries out reaction in 10 hours in NMP (21.2g), NMP (35.3g) and BCS (26.5g), stirring is added 5 hours, obtain aligning agent for liquid crystal (B).
In addition, adding polymerizable compound RM1 0.06g (relative to solid for above-mentioned aligning agent for liquid crystal (B) 10.0g Ingredient is 10 mass %), at room temperature stir to dissolve within 3 hours, prepares aligning agent for liquid crystal (B1).
(embodiment 3)
By PMDA (0.65g, 3.0mmol), DBA (0.46g, 3.0mmol), DA-2 (0.73g, 2.0mmol), DA-3 After (0.93g, 2.0mmol), DA-9 (1.20g, 3.0mmol) carry out reaction in 30 minutes in NMP (15.9g), CBDA is added (1.31g, 7.0mmol), NMP (5.3g), then carries out reacting for 10 hours.NMP (35.2g) and BCS (26.4g), stirring 5 is added Hour, obtain aligning agent for liquid crystal (C).
In addition, adding polymerizable compound RM1 0.06g (relative to solid for above-mentioned aligning agent for liquid crystal (C) 10.0g Ingredient is 10 mass %), at room temperature stir to dissolve within 3 hours, prepares aligning agent for liquid crystal (C1).
(embodiment 4)
By BODA (2.38,10.0mmol), DA-2 (4.39g, 13.0mmol), DA-9 (2.28g, 6.0mmol) in NMP CBDA (1.75g, 9.0mmol) and NMP (10.8g) is added after carrying out reaction in 5 hours at 60 DEG C in dissolution in (32.4g), It carries out reacting for 10 hours at 40 DEG C, obtains polyamic acid solution.
After addition NMP is diluted to 6 mass % in the polyamic acid solution (50g), it is added and is used as imidization catalyst Acetic anhydride (5.4g) and pyridine (2.8g), reacted 3 hours at 50 DEG C.The reaction solution is put into methanol (700ml), Filter out obtained sediment.The sediment is cleaned with methanol, is dried under reduced pressure at 100 DEG C, obtains polyimide powder (D).The acid imide rate of the polyimides is 51%, number-average molecular weight 17000, weight average molecular weight 38000.
NMP (44.0g) is added in obtained polyimide powder (D) (6.0g), stirring 5 hours at 50 DEG C makes it Dissolution.3AMP (1wt%NMP solution) 6.0g, NMP (14.0g), BCS (30.0g) are added in the solution, is stirred at room temperature 5 Hour, to obtain aligning agent for liquid crystal (D1).
In addition, adding polymerizable compound RM1 0.06g (relative to solid for above-mentioned aligning agent for liquid crystal (D1) 10.0g Ingredient is 10 mass %), at room temperature stir to dissolve within 3 hours, prepares aligning agent for liquid crystal (D2).
(embodiment 5)
By BODA (2.38,10.0mmol), DBA (0.87g, 6.0mmol), DA-2 (1.26g, 4.0mmol), DA-3 (1.77g, 4.0mmol), DA-9 (2.28g, 6.0mmol) dissolution in NMP (30.7g), after reacting 5 hours at 60 DEG C, add Enter CBDA (1.68g, 9.0mmol) and NMP (10.2g), is reacted 10 hours at 40 DEG C, obtain polyamic acid solution.
After addition NMP is diluted to 6 mass % in the polyamic acid solution (45g), it is added and is used as imidization catalyst Acetic anhydride (5.1g) and pyridine (2.6g), carried out at 50 DEG C 3 hours react.The reaction solution is put into methanol In (650ml), obtained sediment is filtered out.The sediment is cleaned with methanol, is dried under reduced pressure at 60 DEG C, obtains polyamides Imines powder (E).The acid imide rate of the polyimides is 52%, number-average molecular weight 13000, weight average molecular weight 27000.
NMP (44.0g) is added in obtained polyimide powder (E) (6.0g), stirring 5 hours at 50 DEG C makes it Dissolution.3AMP (1wt%NMP solution) 6.0g, NMP (14.0g), BCS (30.0g) are added into the solution, carries out 5 at room temperature Hour stirring, to obtain aligning agent for liquid crystal (E1).
In addition, adding polymerizable compound RM1 0.06g (relative to solid for above-mentioned aligning agent for liquid crystal (E1) 10.0g Ingredient is 10 mass %), at room temperature stir to dissolve within 3 hours, prepares aligning agent for liquid crystal (E2).
In addition, adding polymerizable compound RM2 0.06g (relative to solid for above-mentioned aligning agent for liquid crystal (E1) 10.0g Ingredient is 10 mass %), at room temperature stir to dissolve within 3 hours, prepares aligning agent for liquid crystal (E3).
(embodiment 6)
By TCA (2.13,10.0mmol), 3AMPDA (1.84g, 8.0mmol), DA-1 (2.04g, 6.0mmol), DA-8 (2.98g, 6.0mmol) dissolution in NMP (32.0g), after reaction in 5 hours is carried out at 80 DEG C, addition CBDA (1.68g, It 9.0mmol) with NMP (10.7g), carries out reacting for 10 hours at 40 DEG C, obtains polyamic acid solution.
After addition NMP is diluted to 6 mass % in the polyamic acid solution (45g), it is added and is used as imidization catalyst Acetic anhydride (4.9g) and pyridine (2.5g), carried out at 50 DEG C 3 hours react.The reaction solution is put into methanol In (650ml), obtained sediment is filtered out.The sediment is cleaned with methanol, is dried under reduced pressure at 60 DEG C, obtains polyamides Imines powder (F).The acid imide rate of the polyimides is 50%, number-average molecular weight 16000, weight average molecular weight 33000.
NMP (44.0g) is added in obtained polyimide powder (F) (6.0g), stirring 5 hours at 50 DEG C makes it Dissolution.3AMP (1wt%NMP solution) 6.0g, NMP (14.0g), BCS (30.0g) are added into the solution, carries out 5 at room temperature Hour stirring, to obtain aligning agent for liquid crystal (F1).
In addition, adding polymerizable compound RM1 0.06g (relative to solid for above-mentioned aligning agent for liquid crystal (F1) 10.0g Ingredient is 10 mass %), at room temperature stir to dissolve within 3 hours, prepares aligning agent for liquid crystal (F2).
(comparative example 1)
By CBDA (1.86g, 10.0mmol), m-PDA (0.76g, 7.0mmol), DA-9 (1.14g, 3.0mmol) in NMP After carrying out reaction in 10 hours in (15.1g), NMP (25.1g) and BCS (18.8g) is added, stirs 5 hours, it is molten to obtain polyamic acid Liquid (G).
In addition, adding polymerizable compound RM1 0.06g (relative to solid for above-mentioned aligning agent for liquid crystal (G) 10.0g Ingredient is 10 mass %), at room temperature stir to dissolve within 3 hours, prepares aligning agent for liquid crystal (G1).
(comparative example 2)
By BODA (2.38,10.0mmol), DBA (2.02g, 13.0mmol), DA-9 (2.28g, 6.0mmol) in NMP After carrying out reaction in 5 hours at 80 DEG C CBDA (1.75g, 9.0mmol) and NMP (8.4g) is added, 40 in dissolution in (25.3g) It carries out reacting for 10 hours at DEG C, obtains polyamic acid solution.
After addition NMP is diluted to 6 mass % in the polyamic acid solution (35g), it is added and is used as imidization catalyst Acetic anhydride (4.8g) and pyridine (2.5g), carried out at 50 DEG C 3 hours react.The reaction solution is put into methanol In (500ml), obtained sediment is filtered out.The sediment is cleaned with methanol, is dried under reduced pressure, is gathered at 100 DEG C Acid imide powder (H).The acid imide rate of the polyimides is 50%, number-average molecular weight 18000, and weight average molecular weight is 37000。
NMP (44.0g) is added in obtained polyimide powder (H) (6.0g), stirring 5 hours at 50 DEG C makes it Dissolution.3AMP (1wt%NMP solution) 6.0g, NMP (14.0g), BCS (30.0g) are added into the solution, carries out 5 at room temperature Hour stirring, to obtain aligning agent for liquid crystal (H1).
In addition, adding polymerizable compound RM1 0.06g (relative to solid for above-mentioned aligning agent for liquid crystal (H1) 10.0g Ingredient is 10 mass %), at room temperature stir to dissolve within 3 hours, prepares aligning agent for liquid crystal (H2).
<production of liquid crystal cells>
(embodiment 7)
Using aligning agent for liquid crystal obtained in embodiment 1 (A1), liquid crystal cells are carried out according to following shown such steps Production.Aligning agent for liquid crystal obtained in embodiment 1 (A1) is spun on be formed with Pixel Dimensions be 300 μm of 100 μ m and line/ Space is respectively the ito surface of the ITO electrode substrate of 5 μm of ITO electrode pattern, after 90 seconds dry on 80 DEG C of hot plate, 200 DEG C heated air circulation type baking oven in carry out 30 minutes be burnt into, formed film thickness 100nm liquid crystal orientation film.
In addition, aligning agent for liquid crystal (A1) to be spun on to the ito surface of not formed electrode pattern, dry 90 on 80 DEG C of hot plate It after second, carries out being burnt into for 30 minutes in 200 DEG C of heated air circulation type baking oven, forms the liquid crystal orientation film of film thickness 100nm.
About above-mentioned 2 substrates, after 4 μm of microbead spacers are spread on the liquid crystal orientation film of a substrate, from thereon Printing and sealing agent (the STRUCTBOND XN- that the epoxy resin of solvent type heat-curing type, Mitsui Chemicals, Inc manufacture 1500T).Then, using the formation of another substrate have liquid crystal orientation film side face as inside, with substrate sticking just now Afterwards, make sealant cures, to make dummy cell.By injecting liquid crystal MLC-6608 in decompression injection normal direction dummy cell (trade name of Merck&Co., Inc. manufacture), to make liquid crystal cells.
The response speed of obtained liquid crystal cells is measured by following methods.Then, 20V is being applied to the liquid crystal cells D/C voltage in the state of, from the outsides of the liquid crystal cells, irradiation 10J has passed through the UV of the bandpass filter of 365nm.Then, then Secondary measurement response speed compares the response speed of UV irradiation front and back.In addition, for the unit measurement pixel portion after UV irradiation Pre-tilt angle.Show the result in table 1.
<measuring method of response speed>
Firstly, successively by backlight, be set as the survey that one group of polarizer, light quantity detector of cross Nicols state constitute Determine in device, configures liquid crystal cells between one group of polarizer.At this point, making to form the pattern of the ITO electrode in wired/space opposite In the angle that cross Nicols are in 45 °.Then, the rectangular wave that above-mentioned liquid crystal cells are applied with voltage ± 6V, frequency 1kHz, with showing Variation of the wave device export using the brightness of light quantity detector observation until saturation, brightness when by no applied voltage are set as 0%, the value by the saturation brightness of the voltage of application ± 4V is set as 100%, by brightness from 10% be changed to 90% needed for the time It is set as response speed.
<measurement of pre-tilt angle>
The LCD Analyser LCA-LUV42A manufactured using MEIRYO TECHNICA CORPORATION.
(embodiment 8~14, comparative example 3,4)
Other than replacing aligning agent for liquid crystal (A1) using aligning agent for liquid crystal shown in table 1 respectively, carries out and implement Example 7 similarly operates, and carries out the response speed of UV irradiation front and back and the measurement of pre-tilt angle.These results are shown in table 1 together.
[table 1]
As shown in table 1, it is confirmed in embodiment, also shows inclination angle using the ultraviolet irradiation of wavelength 365nm.It is another Aspect in comparative example, even if including polymerizable compound in liquid crystal orientation film, can not also show sufficient inclination angle.
It is thought that because in the aligning agent for liquid crystal of comparative example, polymerizable compound itself hardly picks up the purple of 365nm Outside line, thus do not have free radical generating unit liquid crystal orientation film in do not have generate for initiated polymerization adequately from By base.On the other hand, it is believed that be because in the aligning agent for liquid crystal of embodiment, also being generated using the ultraviolet light irradiation of long wavelength side Sufficient free radical, therefore in liquid crystal aligning membrane interface, polymerizable compound polymerize, and forms inclination angle.
(embodiment 15)
Aligning agent for liquid crystal (A1) is replaced using aligning agent for liquid crystal (D1), using the liquid crystal containing polymerizable compound, removes this Except carry out operation similarly to Example 7, make liquid crystal cells.In the state for the D/C voltage that the liquid crystal cells are applied with 20V Under, from the outside of liquid crystal cells, irradiation 7J, 15J have passed through the UV of the bandpass filter of 365nm, the response of more each liquid crystal cells Speed.In addition, having carried out the measurement of pre-tilt angle.Show the result in table 2.
(comparative example 5)
Aligning agent for liquid crystal (A1) is replaced using aligning agent for liquid crystal (H1), using the liquid crystal containing polymerizable compound, removes this Except carry out operation similarly to Example 7, make liquid crystal cells.In the state for the D/C voltage that the liquid crystal cells are applied with 20V Under, from the outside of liquid crystal cells, irradiation 7J, 15J have passed through the UV of the bandpass filter of 365nm, the response of more each liquid crystal cells Speed.In addition, having carried out the measurement of pre-tilt angle.
[table 2]
It confirms in case of example 15 as shown in table 2, even if when ultraviolet irradiation amount as little as 7J, it may have fill The raising for the response speed divided and the Forming ability at inclination angle.On the other hand, it confirms in comparative example 5, ultraviolet irradiation amount Almost without inclination angle is shown when few, in order to show inclination angle, a large amount of ultraviolet light is needed to irradiate.
(embodiment 16)
By IPDI (0.89g, 4.0mmol), DA-1 (1.32g, 4.0mmol), DA-6 (1.52g, 4.0mmol), 3AMPDA (0.48g, 2.0mmol) dissolution in the NMP (16.0g), after carrying out reaction in 5 hours, be added CBDA (1.14g, 5.8mmol) and NMP (5.4g), carries out reacting for 10 hours at room temperature, obtains polyureas-amic acid (PU-PAA) solution.The Mn of the polymer is 11000,28000 Mw.
NMP (30.3g) and 3AMP (1 mass %NMP solution 5.4g), BC are added in the PU-PAA solution (26.8g) (26.8g) is diluted to 6 mass %, carries out stirring for 5 hours at room temperature, to obtain aligning agent for liquid crystal (I1).
In addition, adding polymerizable compound RM1 obtained in synthesis example for above-mentioned aligning agent for liquid crystal (I1) 10.0g 0.06g (being 10 mass % relative to solid component), at room temperature stir to dissolve within 3 hours, prepares aligning agent for liquid crystal (I2)。
(embodiment 17)
NMP (44.0g) is added in KIP150 (6.0g), stirring makes it dissolve for 5 hours.NMP is added in the solution (20.0g), BCS (30.0g) are diluted to 6 mass %, carry out stirring for 5 hours at room temperature, to obtain polymer solution (J1).
In turn, for aligning agent for liquid crystal (H1) 7.0g of comparative example 2, polymer solution (J1) 3.0g and polymerism are added Object RM1 0.06g (being 10 mass % relative to solid component) is closed, carrying out stirring in 3 hours at room temperature makes its uniform dissolution, makes Standby aligning agent for liquid crystal (J2).
(embodiment 18)
By BODA (3.0,12.0mmol), 3AMPDA (1.45g, 6.0mmol), DA-6 (4.57g, 12.0mmol), DA-1 (3.96g, 12.0mmol) dissolution in NMP (49.4g), after reaction in 5 hours is carried out at 60 DEG C, addition CBDA (3.47g, It 17.7mmol) with NMP (16.5g), carries out reacting for 10 hours at 40 DEG C, obtains polyamic acid solution.
After addition NMP is diluted to 6 mass % in the polyamic acid solution (80g), it is added and is used as imidization catalyst Acetic anhydride (14.8g) and pyridine (4.6g), carried out at 70 DEG C 3 hours react.The reaction solution is put into methanol In (1060ml), obtained sediment is filtered out.The sediment is cleaned with methanol, is dried under reduced pressure, is gathered at 100 DEG C Acid imide powder (K).The acid imide rate of the polyimides is 72%, Mn 17000, Mw 54000.
NMP (44.0g) is added in obtained polyimide powder (K) (6.0g), stir within 12 hours at 70 DEG C It mixes and makes it dissolve.3AMP (1wt%NMP solution) 6.0g, NMP (14.0g), BCS (30.0g) are added into the solution, in room temperature It is lower stir within 5 hours, to obtain aligning agent for liquid crystal (K1).
In addition, adding polymerizable compound RM1 0.06g (relative to solid for above-mentioned aligning agent for liquid crystal (K1) 10.0g Ingredient is 10 mass %), at room temperature stir to dissolve within 3 hours, prepares aligning agent for liquid crystal (K2).
(comparative example 6)
By BODA (3.0,12.0mmol), 3AMPDA (1.45g, 6.0mmol), DA-6 (4.57g, 12.0mmol), 4DABP (2.55g, 12.0mmol) dissolution in NMP (45.1g), after reaction in 5 hours is carried out at 60 DEG C, addition CBDA (3.47g, It 17.7mmol) with NMP (15.5g), carries out reacting for 10 hours at 40 DEG C, obtains polyamic acid solution.
After addition NMP is diluted to 6 mass % in the polyamic acid solution (70g), it is added and is used as imidization catalyst Acetic anhydride (14.2g) and pyridine (4.4g), carried out at 70 DEG C 3 hours react.The reaction solution is put into methanol In (940ml), obtained sediment is filtered out.The sediment is cleaned with methanol, is dried under reduced pressure, is gathered at 100 DEG C Acid imide powder (L).The acid imide rate of the polyimides is 70%, Mn 14000, Mw 41000.
NMP (44.0g) is added in obtained polyimide powder (L) (6.0g), stir within 12 hours at 70 DEG C It mixes and makes it dissolve.3AMP (1wt%NMP solution) 6.0g, NMP (14.0g), BCS (30.0g) are added into the solution, in room temperature It is lower stir within 5 hours, to obtain aligning agent for liquid crystal (L1).
In addition, adding polymerizable compound RM1 0.06g (relative to solid for above-mentioned aligning agent for liquid crystal (L1) 10.0g Ingredient is 10 mass %), at room temperature stir to dissolve within 3 hours, prepares aligning agent for liquid crystal (L2).
<production and evaluation of liquid crystal cells>
(embodiment 19)
Aligning agent for liquid crystal (A1) is replaced using aligning agent for liquid crystal (I2), in addition to this carries out behaviour similarly to Example 7 Make, compares the response speed of UV irradiation front and back.In addition, having carried out the measurement of pre-tilt angle.
(embodiment 20)
Aligning agent for liquid crystal (A1) is replaced using aligning agent for liquid crystal (J2), in addition to this carries out behaviour similarly to Example 7 Make, compares the response speed of UV irradiation front and back.In addition, having carried out the measurement of pre-tilt angle.
(embodiment 21)
Aligning agent for liquid crystal (A1) is replaced using aligning agent for liquid crystal (K2), in addition to this carries out behaviour similarly to Example 7 Make, compares the response speed of UV irradiation front and back.In addition, having carried out the measurement of pre-tilt angle.
(comparative example 7)
Aligning agent for liquid crystal (A1) is replaced using aligning agent for liquid crystal (L2), in addition to this carries out behaviour similarly to Example 7 Make, compares the response speed of UV irradiation front and back.In addition, having carried out the measurement of pre-tilt angle.
[table 3]
It is confirmed by the result in above-described embodiment 19,20, even if using the backbone structure having in addition to polyimides Polymer (polyurea structure, polystyrene structure), also into side chain position import free radical cause position, to utilize The ultraviolet light irradiation of long wavelength as 365nm also shows sufficient pre-tilt angle.
On the other hand it is found that free radical initiation position to be directed into the main chain backbone of polymer as shown in comparative example 7 When middle, there is the tendency to die down compared with the case where being directed into side chain position in the expressive ability of pre-tilt angle.
Generally, it is considered that being taken using the polymerization reaction that ultraviolet light irradiation reacts polymerizable compound and forms inclination angle in liquid crystal Efficiently occur to the interface of film and the liquid crystal being in contact with it, to form pre-tilt angle.But the free radical as comparative example 7 When position is located in main chain backbone, it is believed that may be because, using ultraviolet light irradiation generate free radical be present in polymer, It can not efficiently participate in reacting with what the interface of liquid crystal occurred.
Industrial availability
Aligning agent for liquid crystal of the invention is served not only as making PSA type liquid crystal display, SC-PVA type liquid crystal display The liquid crystal of equal vertical orientation modes indicates that the aligning agent for liquid crystal of element is useful, but also can be suitably used for passing through friction Processing, light orientation processing and the purposes of liquid crystal orientation film made.
It should be noted that quoting Japanese Patent filed on September 3rd, 2013 herein goes out saying for hope 2013-182351 Bright book, claims, attached drawing and abstract of description full content, be incorporated as a disclosure of the specification of the present invention.

Claims (18)

1. a kind of aligning agent for liquid crystal, which is characterized in that containing the polymer with side-chain structure shown in following formula (I)s,
Ar indicates the aromatic hydrocarbyl in phenylene, naphthylene and biphenylene, is optionally substituted on these alkyl organic Group, hydrogen atom are optionally substituted with halogen atoms, R1、R2It is separately alkyl, alkoxy, the benzyl of carbon atom number 1~10 Or phenethyl, in the case where alkyl and/or alkoxy, optionally by R1、R2Form ring, T1、T2Be separately singly-bound ,- O-、-COO-、-OCO-、-NHCO-、-CONH-、-NH-、-CH2O-、-N(CH3)-、-CON(CH3)-or-N (CH3) CO-, S is single Key or the alkylidene of carbon atom number 1~20 that is unsubstituted or the being replaced by fluorine atoms, wherein-CH of alkylidene2Or CF2Appoint Selection-CH=CH- displacement, in addition, optionally being replaced by these groups in the case where following any group is not adjacent to each other :- O- ,-COO- ,-OCO- ,-NHCO- ,-CONH- ,-NH-, divalent carbocyclic ring or bivalent heterocyclic, Q indicate following structures,
-OR
R indicates the alkyl of hydrogen atom or carbon atom number 1~4, R3Expression-CH2,-NR- ,-O- or-S-.
2. aligning agent for liquid crystal according to claim 1, wherein the polymer with side-chain structure shown in formula (I) For selected from as with side-chain structure shown in the formula (I) polyimide precursor and by polyamides obtained from its imidizate Asia At least one of the group of amine composition polymer.
3. aligning agent for liquid crystal according to claim 1 or 2, wherein the Ar in formula (I) is phenylene, and Q is-OR.
4. aligning agent for liquid crystal according to claim 1 or 2, wherein the polymer also has and makes liquid crystal vertical-tropism Side chain.
5. aligning agent for liquid crystal according to claim 4, wherein the side chain for making liquid crystal vertical-tropism is selected from following formula (II-1) and at least one of (II-2),
X1Indicate singly-bound ,-(CH2)a-、-O-、-CH2O- ,-COO- or OCO-, the integer that wherein a is 1~15, X2Indicate singly-bound or (CH2)b, the integer that wherein b is 1~15, X3Indicate singly-bound ,-(CH2)c-、-O-、-CH2O- ,-COO- or OCO-, wherein c is 1 ~15 integer, X4Indicate bivalent cyclic group in phenyl ring, cyclohexane ring and heterocycle, these cyclic groups it is arbitrary Hydrogen atom optionally by the alkyl of carbon number 1~3, the alkoxy of carbon number 1~3, carbon number 1~3 containing fluoroalkyl, carbon number 1~3 it is fluorine-containing Alkoxy or fluorine atom replace, and X4Two in organic group optionally selected from the carbon number 17~51 with steroid skeleton Valence organic group, X5Indicate the bivalent cyclic group in phenyl ring, cyclohexane ring and heterocycle, it is any on these cyclic groups Hydrogen atom optionally contained by the alkyl of carbon number 1~3, the alkoxy of carbon number 1~3, carbon number 1~3 containing fluoroalkyl, carbon number 1~3 Fluoroalkyloxy or fluorine atom replace, and n indicates 0~4 integer, X6Indicate that the alkyl of carbon number 1~18, carbon number 1~18 contain fluothane The fluoroalkoxy of base, the alkoxy of carbon number 1~18 or carbon number 1~18,
-x7-x8 [II-2]
X7Indicate singly-bound ,-O- ,-CH2O-、-CONH-、-NHCO-、-CON(CH3)-、-N(CH3) CO- ,-COO- or OCO-, X8Table Show carbon number 8~22 alkyl or carbon number 6~18 containing fluoroalkyl.
6. aligning agent for liquid crystal according to claim 1 or 2, wherein the polymer, which also has, contains light reaction in structure The side chain of property group.
7. aligning agent for liquid crystal according to claim 6, wherein the side chain in the structure containing photoreactive group is under Stating formula (III) or formula (IV) indicates,
-R8-R9-R10 [III]
R8Indicate singly-bound ,-CH2-、-O-、-COO-、-OCO-、-NHCO-、-CONH-、-NH-、-CH2O-、-N(CH3)-、-CON (CH3)-or-N (CH3) CO-, R9The alkylidene of expression singly-bound, the carbon number 1~20 being optionally replaced by fluorine atoms, alkylidene- CH2Optional use-CF2Or-CH=CH- is arbitrarily replaced, in the case where following any group is not adjacent to each other optionally by this A little group displacements :-O- ,-COO- ,-OCO- ,-NHCO- ,-CONH- ,-NH-, divalent carbocyclic ring or heterocycle, R10It indicates selected from following Photoreactive group in formula,
-Y1-Y2-Y3-Y4-Y5-Y6 (IV)
Y1Expression-CH2,-O- ,-CONH- ,-NHCO- ,-COO- ,-OCO- ,-NH- or-CO-, Y2For the alkylene of carbon number 1~30 Base, divalent carbocyclic ring perhaps the heterocycle alkylidene, divalent carbocyclic ring or heterocycle one or more hydrogen atoms optionally by fluorine atom or Person's organic group replaces, Y2- the CH in the case where following group is not adjacent to each other2Optionally replaced by these groups :-O- ,- NHCO- ,-CONH- ,-COO- ,-OCO- ,-NH- ,-NHCONH- ,-CO-, Y3Expression-CH2-、-O-、-CONH-、-NHCO-、- COO- ,-OCO- ,-NH- ,-CO- or singly-bound, Y4Indicate cinnamoyl, Y5For singly-bound, the alkylidene of carbon number 1~30, divalent carbocyclic ring Perhaps one or more hydrogen atoms of the heterocycle alkylidene, divalent carbocyclic ring or heterocycle are optionally taken by fluorine atom or organic group Generation, Y5- the CH in the case where following group is not adjacent to each other2Optionally replaced by these groups :-O- ,-NHCO- ,-CONH- ,- COO- ,-OCO- ,-NH- ,-NHCONH- ,-CO-, Y6It indicates polymerism group, is acryloyl group or methylacryloyl.
8. aligning agent for liquid crystal according to claim 1 or 2, wherein the polymer contains: making containing following formula (1) institute The diamine component of the diamines shown is reacted with tetracarboxylic dianhydride's ingredient to be obtained polyimide precursor and obtains its imidizate At least one of polyimides polymer,
The definition of symbol in formula is identical as above-mentioned formula (I).
9. aligning agent for liquid crystal according to claim 8, wherein the polymer also contains: making containing shown in following formula (2) Diamines diamine component reacted with tetracarboxylic dianhydride's ingredient obtained from polyimide precursor and its imidizate is obtained At least one of polyimides polymer,
X indicates the structure of above-mentioned formula [II-1] or formula [II-2], and n indicates 1~4 integer.
10. aligning agent for liquid crystal according to claim 8, wherein the polymer also contains: make containing following formula (3) or Polyimide precursor obtained from the diamine component of diamines shown in formula (4) is reacted with tetracarboxylic dianhydride's ingredient and by its acid imide At least one of polyimides polymer obtained from change,
R8、R9And R10Definition it is identical as above-mentioned formula (III),
The definition of Y1, Y2, Y3, Y4, Y5 and Y6 are identical as above-mentioned formula (IV).
11. aligning agent for liquid crystal according to claim 8, wherein diamines shown in (1) is the 10 of whole diamine components Mole %~80 mole %.
12. aligning agent for liquid crystal according to claim 1 or 2, wherein aligning agent for liquid crystal is used in liquid crystal and/or liquid crystal In alignment films containing polymerizable compound and side apply the irradiation of voltage lateral dominance ultraviolet light make the polymerizable compound react and Obtained liquid crystal indicates element.
13. a kind of liquid crystal orientation film, the aligning agent for liquid crystal as described in any one of claim 1~12 is obtained.
14. a kind of liquid crystal indicates element, has liquid crystal orientation film described in claim 13.
15. liquid crystal according to claim 14 indicates element, wherein liquid crystal indicates that element is that side applies voltage lateral dominance purple Obtained from outside line irradiation reacts the polymerizable compound contained in liquid crystal and/or in liquid crystal orientation film.
16. a kind of polymer, for selected from as the polyimide precursor with side-chain structure shown in following formula (I)s and by its acyl At least one of the group of the composition of polyimides obtained from imidization,
R1、R2、T1、T2, the definition of S and Q it is identical as formula (I) in claim 2.
17. a kind of diamines is indicated by following formula (I)s,
In formula, R1、R2、T1、T2, the definition of S, Q, R it is identical as above-mentioned formula (I).
18. a kind of diamines, is indicated by following formula,
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